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Office of Scientific and Technical Information
Electrospray Ionization Mass Spectrometry
SciTech Connect (OSTI)
Electrospray Ionization (ESI) is a process whereby gas phase ions are created from molecules in solution. As a solution exits a narrow tube in the presence of a strong electric field, an aerosol of charged droplets are is formed that produces gas phase ions as they it desolvates. ESI-MS comprises the creation of ions by ESI and the determination of their mass to charge ratio (m/z) by MS.
Kelly, Ryan T.; Marginean, Ioan; Tang, Keqi
Tissue Imaging Using Nanospray Desorption Electrospray Ionization Mass Spectrometry
We present the first results showing the ambient imaging of biological samples in their native environment using nanospray desorption ionization (nanoDESI) mass spectrometry. NanoDESI is an ambient pressure ionization technique that enables precise control of ionization of molecules from substrates. We demonstrate highly sensitive and robust analysis of tissue samples with high spatial resolution (<12 {mu}m) without sample preparation, which will be essential for applications in clinical diagnostics, drug discovery, molecular biology, and biochemistry.
Laskin, Julia; Heath, Brandi S.; Roach, Patrick J.; Cazares, Lisa H.; Semmes, O. John
Subcellular analysis by laser ablation electrospray ionization mass spectrometry
DOE Patents [OSTI]
In various embodiments, a method of laser ablation electrospray ionization mass spectrometry (LAESI-MS) may generally comprise micro-dissecting a cell comprising at least one of a cell wall and a cell membrane to expose at least one subcellular component therein, ablating the at least one subcellular component by an infrared laser pulse to form an ablation plume, intercepting the ablation plume by an electrospray plume to form ions, and detecting the ions by mass spectrometry.
Vertes, Akos; Stolee, Jessica A; Shrestha, Bindesh
Electrospray Ionization Mass Spectrometry of hexanitrohexaazaisowurtzitane (CL-20)
Hexanitrohexaazaisowurtzitane, (C6H6N12O12, MW 438) {CL-20}, is a high-energy propellent that has been recently developed and successfully tested (Nielsen et al. 1998). CL-20 releases more energy on ignition and is more stable to accidental detonation than currently used energetic materials. It is expected to replace many of the energetic materials currently being used by the Department of Defense (DoD). The EPA method 8330 (EPA 1997) for the analysis of explosives and metabolites in soils calls for the use of UV/Vis detection. High performance liquid chromatography has been used to quantify CL-20 and precursor concentration (Bazaki et al. 1998`) at relatively high concentrations. Fourier transform infrared (FTIR) spectroscopy has been used to identify different crystal forms of CL-20 (4 isomers; Kim et al. 1998). Campbell et al. (1997) utilized particle beam mass spectrometry for the analysis of enzymatic degradation of explosives. Introduction and recent improvements of ionization techniques such as electrospray (ES) have allowed the mass spectrometer to become more widely used in liquid chromatography. Schilling(1996) also examined explosive components and metabolites using electrospray (ES) and atmospheric pressure chemical ionization (APCI) liquid chromatography/mass spectrometry (LC/MS). Schilling�s results showed that compared to thermospray LC/MS, APCI and ES were more sensitive than thermospray by at least an order of magnitude. 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), 10 nitroso-RDX metabolites, and other munitions in ground water have been analyzed using solid phase extraction and isotope dilution liquid chromatography-APCI mass spectrometry (Cassada et al. 1999). The method detection limits indicate that nitramine and nitroaromatic compounds can be routinely determined in ground water samples using electrospray LC/MS with concentration techniques utilizing solid-phase extraction. Miller et al. (1996) studied nitrated explosives with mobile phase additives to enhance the ESI intensities and spectral consistencies. Several of the explosives gave nitrate adduct ions in the negative mode with ammonium nitrate as the mobile phase. The nitramines RDX and 1,3,5,7-tetranitro-1,3,5,7 tetraazacyclooctane (HMX) showed the greatest enhancement in response of the explosives. Ammonium nitrate was used as the mobile phase and made it possible to obtain consistent and interpretable LC/MS spectra at the nanogram level. Campbell et al. (1999), Shi et al. (2000), and Goheen et al. (1999) utilized electrospray ionization mass spectrometry for the identification of degradation products of explosives. Yinon et al. (1997) used ESI and tandem mass spectrometry collision-induced dissociation to examine several nitramine compounds including trinitrotolutene (TNT), RDX, and pentaerythritol tetranitrate (PETN). The results indicate that explosives can be detected in the negative ion mode and characterized by various adduct ions. As an example, for nitroglycerin, the major adduct ion observed was (M+ONO2)-. In addition, Harvey et al. (1992) have used direct probe mass spectrometry for the analysis of degradation products of tetryl and its transformation products in soil. The negative ion electrospray mass spectrum of CL-20 is reported here. The major adduct ions observed under negative ion conditions were (M+Cl)- at m/z 473 and (M+ONO2) � at m/z 500. In addition, the results of mass spectrometry/mass spectrometry studies are also discussed.
Campbell, James A.; Szecsody, Jim E.; Devary, Brooks J.; Valenzuela, Blandina R.
Analysis of perchlorate in groundwater by electrospray ionization mass spectrometry/mass spectrometry
An electrospray ionization mass spectrometry/mass spectrometry (ESI/MS/MS) method was developed to measure part-per-billion ({micro}g/L) concentrations of perchlorate in groundwater. Selective and sensitive perchlorate detection was achieved by operating the mass spectrometer in the negative ionization mode and by using MS/MS to monitor the CIO{sub 4}{sup {minus}} to ClO{sub 3}{sup {minus}} transition. The method of standard additions was used to address the considerable signal suppression caused by anions that are typically present in groundwater, such as bicarbonate and sulfate. ESI-MS/MS analysis was rapid, accurate, reproducible, and provided a detection limit of 0.5 {micro}g/L perchlorate in groundwater. Accuracy and precision of the ESI/MS/MS method were assessed by analyzing performance evaluation samples in a groundwater matrix and by comparing ion chromatography (IC) and ESI/MS/MS results for local groundwater samples. Results for the performance evaluation samples differed from the certified values by 4--13%, and precision ranged from 3 to 10% (relative standard deviation). The IC and ESI/MS/MS results were statistically indistinguishable for perchlorate concentrations above the detection limits of both methods.
Koester, C.J.; Beller, H.R.; Halden, R.U.
New developments in biochemical mass spectrometry: Electrospray ionization
The principles, development, and recent application of electrospray ionization-mass spectrometry (ESI-MS) to biological compounds are reviewed. ESI-MS methods now allow determination of accurate molecular weights for proteins extending to over 50,000, and in some cases well over 100,000. Similar capabilities are being developed for oligonucleotides. The instrumentation used for ESI-MS is briefly described and it is shown that, although ionization efficiency appears to be uniformly high, detector sensitivity may be directly correlated with molecular weight. The use of tandem mass spectrometry (e.g., MS/MS) for extending collision-induced dissociation (CID) methods to the structural studies of large molecules is described. For example, effective CID of various albumin species (molecular weight {approximately}66,000) can be obtained, far larger than obtainable for singly charged molecular ions. The combination of capillary electrophoresis, in both free solution zone electrophoresis and isotachophoresis formats, as well as microcolumn liquid chromatography with ESI-MS, provides the capability for on-line separation and analysis of subpicomole quantities of proteins. These and other new developments related to ESI-MS are illustrated by a range of examples. Fundamental considerations suggest even more impressive developments may be anticipated related to detection sensitivity and methods for obtaining structural information.
Smith, R.D.; Loo, J.A.; Edmonds, C.G.; Barinaga, C.J.; Udseth, H.R. (Pacific Northwest Laboratory, Richland, WA (USA))
Detection of methoxylated anions of fullerenes by electrospray ionization mass spectrometry
Electrospray ionization mass spectrometry (ESI-MS) has been applied to the study of the reactions of fullerenes in solution. The C[sub 60][sup [minus
Wilson, S.R.; Wu, Y. (New York Univ., NY (United States))
Three-dimensional molecular imaging by infrared laser ablation electrospray ionization mass spectrometry
The field of the invention is atmospheric pressure mass spectrometry (MS), and more specifically a process and apparatus which combine infrared laser ablation with electrospray ionization (ESI).
Vertes, Akos (Reston, VA); Nemes, Peter (Silver Spring, MD)
Laser ablation electrospray ionization (LAESI) for atmospheric pressure, In vivo, and imaging mass spectrometry
The field of the invention is atmospheric pressure mass spectrometry (MS), and more specifically a process and apparatus which combine infrared laser ablation (LA) with electrospray ionization (ESI).
Laser ablation electrospray ionization (LAESI) for atmospheric pressure, in vivo, and imaging mass spectrometry
Vertes, Akos; Nemes, Peter
Evaluation of histone sequence and modifications by electrospray ionization mass spectrometry and tandem mass spectrometry
The histones, together with other specialized proteins and DNA, form the extraordinarily complex structure of chromatin. Electrospray ionization (ESI) permits the promotion of such protein species into the gas phase as intact, multiply charged molecular species. Mass spectrometry (MS), using a linear quadrupole mass filter, permits measurement of the relative molecular mass of these intact species with precision and accuracy. The latter are sufficient to evaluate variations in the primary structure of the histones and the type and extent of the natural and induced multiple covalent modifications. The locations of modifications are revealed by tandem mass spectrometry using tandem linear quadrupole or ion trap instruments on the intact species or the modified peptides derived by selective proteolysis. Experiments in applying this technique to histones from K562, a human-derived cell line, have demonstrated variations in the profile of modification through the normal cell cycle and in the presence of agents that inhibit enzymes responsible for reversal of the modification. The authors are currently testing the hypothesis that ESI-MS will permit the sensitive and selective identification of insult-induced modifications, distinguishing them from natural cell-cycle changes. This will be possible because ESI-MS reveals the full details of the profile of multiple posttranslational modifications of histones.
Edmonds, C.G.; Loo, J.A.; Smith, R.D.; Fuciarelli, A.F.; Thrall, B.D.; Morris, J.E.; Springer, D.L. (Pacific Northwest Lab., Richland, WA (United States))
Explorations of Functionalized Gold Nanoparticle Surface Chemistry for Laser Desorption Ionization Mass Spectrometry Applications
E-Print Network [OSTI]
EXPLORATIONS OF FUNCTIONALIZED GOLD NANOPARTICLE SURFACE CHEMISTRY FOR LASER DESORPTION IONIZATION MASS SPECTROMETRY APPLICATIONS A Thesis by MARIO ESTUARDO GOMEZ HERNANDEZ Submitted to the Office... DESORPTION IONIZATION MASS SPECTROMETRY APPLICATIONS A Thesis by MARIO ESTUARDO GOMEZ HERNANDEZ Submitted to the Office of Graduate Studies of Texas A&M University in partial fulfillment of the requirements for the degree...
Gomez Hernandez, Mario 1980-
High-Resolution Electrospray Ionization Mass Spectrometry Analysis...
Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)
Mass Spectrometry Analysis of Water- Soluble Organic Aerosols Collected with a Particle Abstract: This work demonstrates the utility of a particle-into-liquid sampler (PILS) a...
A postsource decay study of bradykinin by Matrix-assisted laser desorption ionization mass spectrometry
Matrix-assisted laser desorption/ionization (MALDI) with time-of-flight (TOF) mass spectrometry is a very powerful technique for the analysis of peptides and proteins. Fragmentation reactions of the protonated analyte molecule, [M+H]+ ions...
Wei, Xiaona
The effect of solvent on matrix-assisted laser desorption ionization mass spectrometry
Since its introduction in 1988, matrix-assisted laser desorption/ionization mass spectrometry (MALDI) has developed into a useful analytical tool in the biological field. The work presented here focuses on the effect of solvent on MALDI ion yields...
Campo, Karen Kay
Ionization and transmission efficiency in an electrospray ionization-mass spectrometry interface
The efficiency of sample ionization by electrospray ionization (ESI) and the transmission of the charged droplets and gas-phase ions through an ESI interface were investigated in order to advance the understanding of how these factors affect mass spectrometry (MS) sensitivity. In addition, the effects of the ES emitter distance to the inlet, solution flow rate, and inlet temperature to the ionization and transmission efficiency were characterized. Quantitative measurements of ES current loss throughout the ESI interface were accomplished by electrically isolating the front surface of the interface from the inner wall of the heated inlet capillary, enabling losses on the two surfaces to be distinguished. The ES current lost to the front surface of the ESI interface was also spatially profiled with a linear array of 340-�m-dia. electrodes placed adjacent to the inlet capillary entrance. Current transmitted as gas-phase ions was differentiated from charged droplets and solvent clusters by directly measuring sensitivity with a single quadrupole mass spectrometer. The study has revealed a large sampling efficiency into the inlet capillary (>90% at an emitter distance of 1 mm), a global rather than a local gas dynamic effect on the shape of the ES plume due to the gas flow conductance limit of the inlet capillary, a large (>80%) loss of analyte after transmission through the inlet due to incomplete desolvation at a solution flow rate of 1.0 �L/min, and a decrease in analyte peak intensity at lower temperatures, despite a large increase in ES current transmission efficiency. These studies provide a clearer understanding of the parameters affecting ion transmission into the mass spectrometer, and will serve to guide the design of more efficient instrument interfaces.
Page, Jason S.; Kelly, Ryan T.; Tang, Keqi; Smith, Richard D.
Direct analysis of samples by mass spectrometry: From elements to bio-molecules using laser ablation inductively couple plasma mass spectrometry and laser desorption/ionization mass spectrometry
Mass spectrometric methods that are able to analyze solid samples or biological materials with little or no sample preparation are invaluable to science as well as society. Fundamental research that has discovered experimental and instrumental parameters that inhibit fractionation effects that occur during the quantification of elemental species in solid samples by laser ablation inductively coupled plasma mass spectrometry is described. Research that determines the effectiveness of novel laser desorption/ionization mass spectrometric methods for the molecular analysis of biological tissues at atmospheric pressure and at high spatial resolution is also described. A spatial resolution is achieved that is able to analyze samples at the single cell level.
Perdian, David C.
Spatially resolved thermal desorption/ionization coupled with mass spectrometry
A system and method for sub-micron analysis of a chemical composition of a specimen are described. The method includes providing a specimen for evaluation and a thermal desorption probe, thermally desorbing an analyte from a target site of said specimen using the thermally active tip to form a gaseous analyte, ionizing the gaseous analyte to form an ionized analyte, and analyzing a chemical composition of the ionized analyte. The thermally desorbing step can include heating said thermally active tip to above 200.degree. C., and positioning the target site and the thermally active tip such that the heating step forms the gaseous analyte. The thermal desorption probe can include a thermally active tip extending from a cantilever body and an apex of the thermally active tip can have a radius of 250 nm or less.
Jesse, Stephen; Van Berkel, Gary J; Ovchinnikova, Olga S
High-Speed Tandem Mass Spectrometric in Situ Imaging by Nanospray Desorption Electrospray Ionization Mass Spectrometry
Nanospray desorption electrospray ionization (nano-DESI) combined with tandem mass spectrometry (MS/MS), high-resolution mass analysis (m/m=17,500 at m/z 200), and rapid spectral acquisition enabled simultaneous imaging and identification of more than 300 molecules from 92 selected m/z windows (� 1 Da) with a spatial resolution of better than 150 um. Uterine sections of implantation sites on day 6 of pregnancy were analyzed in the ambient environment without any sample pre-treatment. MS/MS imaging was performed by scanning the sample under the nano-DESI probe at 10 um/s while acquiring higher-energy collision-induced dissociation (HCD) spectra for a targeted inclusion list of 92 m/z values at a rate of ~6.3 spectra/s. Molecular ions and their corresponding fragments, separated using high-resolution mass analysis, were assigned based on accurate mass measurement. Using this approach, we were able to identify and image both abundant and low-abundance isobaric species within each m/z window. MS/MS analysis enabled efficient separation and identification of isobaric sodium and potassium adducts of phospholipids. Furthermore, we identified several metabolites associated with early pregnancy and obtained the first 2D images of these molecules.
Lanekoff, Ingela T.; Burnum-Johnson, Kristin E.; Thomas, Mathew; Short, Joshua TL; Carson, James P.; Cha, Jeeyeon; Dey, Sudhansu K.; Yang, Pengxiang; Prieto Conaway, Maria C.; Laskin, Julia
High explosives vapor detection by atmospheric sampling glow discharge ionization/tandem mass spectrometry
The combination of atmospheric sampling glow discharge ionization with tandem mass spectrometry for the detection of traces of high explosives is described. Particular emphasis is placed on use of the quadrupole ion trap as the type of tandem mass spectrometer. Atmospheric sampling glow discharge provides a simple, rugged, and efficient means for anion formation while the quadrupole ion trap provides for efficient tandem mass spectrometry. Mass selective ion accumulation and non-specific ion activation methods can be used to overcome deleterious effects arising from ion/ion interactions. Such interactions constitute the major potential technical barrier to the use of the ion trap for real-time monitoring of targeted compounds in uncontrolled and highly variable matrices. Tailored waveforms can be used to effect both mass selective ion accumulation and ion activation. Concatenated tailored waveforms allow for both functions in a single experiment thereby providing the capability for monitoring several targeted species simultaneously. The combination of atmospheric sampling glow discharge ionization with a state-of-the-art analytical quadrupole ion trap is a highly sensitive and specific detector for traces of high explosives. The combination is also small and inexpensive relative to virtually any other form of tandem mass spectrometry. The science and technology underlying the glow discharge/ion trap combination is sufficiently mature to form the basis for an engineering effort to make the detector portable. 85 refs.
McLuckey, S.A.; Goeringer, D.E.; Asano, K.G. [Oak Ridge National Lab., TN (United States). Chemical and Analytical Sciences Div.
Plume collimation for laser ablation electrospray ionization mass spectrometry
In various embodiments, a device may generally comprise a capillary having a first end and a second end; a laser to emit energy at a sample in the capillary to ablate the sample and generate an ablation plume in the capillary; an electrospray apparatus to generate an electrospray plume to intercept the ablation plume to produce ions; and a mass spectrometer having an ion transfer inlet to capture the ions. The ablation plume may comprise a collimated ablation plume. The device may comprise a flow cytometer. Methods of making and using the same are also described.
Vertes, Akos; Stolee, Jessica A.
Elemental and isotopic analysis of inorganic salts by laser desorption ionization mass spectrometry
Laser desorption ionization mass spectrometry is applied for the analysis of elements as well as their isotopic composition in different inorganic salts. At very low laser energies the inorganic ions are desorbed and ionized from the thin layer of the sample surface. The naturally occurring isotopes of alkali and silver ions are resolved using time of flight mass spectrometer. Further increase in laser energy shows the appearance of Al, Cr, and Fe ions in the mass spectra. This indicates the penetration laser beam beyond the sample surface leading to the ablation of sample target at higher energies. The simultaneous appearance of atomic ions from the sample target at relatively higher laser energies hampers the unambiguous identification of amino acid residues from the biomolecular ions in MALDI-MS.
Jayasekharan, T.; Sahoo, N. K. [Applied Spectroscopy Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India)
High-Resolution Desorption Electrospray Ionization Mass Spectrometry for Chemical Characterization of Organic Aerosols
Characterization of the chemical composition and chemical transformations of secondary organic aerosol (SOA) is both a major challenge and the area of greatest uncertainty in current aerosol research. This study presents the first application of desorption electrospray ionization combined with high-resolution mass spectrometry (DESI-MS) for detailed chemical characterization and studies of chemical aging of OA collected on Teflon substrates. DESI-MS offers unique advantages both for detailed characterization of chemically labile components in OA that cannot be detected using more traditional electrospray ionization mass spectrometry (ESI-MS) and for studying chemical aging of OA. DESI-MS enables rapid characterization of OA samples collected on substrates by eliminating the sample preparation stage. In addition, it enables detection and structural characterization of chemically labile molecules in OA samples by minimizing the residence time of analyte in the solvent. SOA produced by the ozonolysis of limonene (LSOA) was allowed to react with gaseous ammonia. Chemical aging resulted in measurable changes in the optical properties of LSOA observed using UV- visible spectroscopy. DESI-MS combined with tandem mass spectrometry experiments (MS/MS) enabled identification of species in aged LSOA responsible for absorption of the visible light. Detailed analysis of the experimental data allowed us to identify chemical changes induced by reactions of LSOA constituents with ammonia and distinguish between different mechanisms of chemical aging.
Laskin, Julia; Laskin, Alexander; Roach, Patrick J.; Slysz, Gordon W.; Anderson, Gordon A.; Nizkorodov, Serguei; Bones, David L.; Nguyen, Lucas
Quantifying Uranium Isotope Ratios Using Resonance Ionization Mass Spectrometry: The Influence of Laser Parameters on Relative Ionization Probability
Resonance Ionization Mass Spectrometry (RIMS) has been developed as a method to measure relative uranium isotope abundances. In this approach, RIMS is used as an element-selective ionization process to provide a distinction between uranium atoms and potential isobars without the aid of chemical purification and separation. We explore the laser parameters critical to the ionization process and their effects on the measured isotope ratio. Specifically, the use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of {sup 235}U/{sup 238}U ratios to decrease laser-induced isotopic fractionation. By broadening the bandwidth of the first laser in a 3-color, 3-photon ionization process from a bandwidth of 1.8 GHz to about 10 GHz, the variation in sequential relative isotope abundance measurements decreased from >10% to less than 0.5%. This procedure was demonstrated for the direct interrogation of uranium oxide targets with essentially no sample preparation. A rate equation model for predicting the relative ionization probability has been developed to study the effect of variation in laser parameters on the measured isotope ratio. This work demonstrates that RIMS can be used for the robust measurement of uranium isotope ratios.
Isselhardt, B H
Characterization of the microdialysis junction interface for capillary electrophoresis/microelectrospray ionization mass spectrometry
A capillary electrophoresis/electrospray ionization mass spectrometry (CE/ESI-MS) interface, based on an electric circuit across a microdialysis membrane surrounding a short capillary segment closely connected to the separation capillary terminus, is demonstrated to be sensitive, efficient, and rugged. A microspray type ionization emitter produces a stable electrospray at the low flow rates provided by CE and thus avoids both the need for a makeup liquid flow provided by liquid junction or sheath flow interfaces and the subsequent dilution and reduction in sensitivity. Reproducibility studies and comparisons with CE/UV and the CE/sheath flow interface with ESI-MS are presented. Additionally, postrun acidification via the microdialysis junction interface is demonstrated and shown to be capable of denaturing the holomyoglobin protein noncovalent complex while maintaining separation efficiency. 21 refs., 7 figs., 1 tab.
Severs, J.C.; Smith, R.D. [Pacific Northwest National Lab., Richland, WA (United States)] [Pacific Northwest National Lab., Richland, WA (United States)
Shotgun Approach for Quantitative Imaging of Phospholipids Using Nanospray Desorption Electrospray Ionization Mass Spectrometry
Mass spectrometry imaging (MSI) has been extensively used for determining spatial distributions of molecules in biological samples, and there is increasing interest in using MSI for quantification. Nanospray desorption electrospray ionization, or nano-DESI, is an ambient MSI technique where a solvent is used for localized extraction of molecules followed by nanoelectrospray ionization. Doping the nano-DESI solvent with carefully selected standards enables online quantification during MSI experiments. In this proof-of-principle study, we demonstrate this quantification approach can be extended to provide shotgun-like quantification of phospholipids in thin brain tissue sections. Specifically, two phosphatidylcholine (PC) standards were added to the nano-DESI solvent for simultaneous imaging and quantification of 22 PC species observed in nano-DESI MSI. Furthermore, by combining the quantitative data obtained in the individual pixels, we demonstrate quantification of these PC species in seven different regions of a rat brain tissue section.
Lanekoff, Ingela T.; Thomas, Mathew; Laskin, Julia
Biases in Ion Transmission Through an Electrospray Ionization-Mass Spectrometry Capillary Inlet
The standard heated capillary inlet of an electrospray ionization mass spectrometry (ESI-MS) interface was compared with shorter versions of the inlet to determine the effects on transmission and ionization efficiencies for low-flow electrosprays. The primary finding of the study was a large bias towards higher mobility species in the electrospray current losses to the inside walls of the inlet. The transmission efficiency increased with decreasing capillary length due to reduced losses along the capillary. A decrease in transmission efficiency was also confirmed for electrosprays of higher conductivity solvents. A direct correlation between mass spectrometry sensitivity and the transmitted electrospray current was not observed as some analytes showed little to no increase in sensitivity while others showed as high as a 15 � fold increase. The variation was shown to at least be partially dependent on the analytes� mobilities. Higher mobility analytes demonstrated a larger increase in sensitivity when shorter inlets were used. The results indicate that considerable biases against higher mobility species can be produced by the use of long capillary inlets in the ESI-MS interface and strategies are provided to minimize the bias against higher mobility species for efficient ion transmission through the heated capillary interface.
Page, Jason S.; Marginean, Ioan; Baker, Erin Shammel; Kelly, Ryan T.; Tang, Keqi; Smith, Richard D.
On-line microdialysis sample cleanup for electrospray ionization mass spectrometry of nucleic acid samples
A major limitation of electrospray ionization mass spectrometry (ESI-MS) for oligonucleotide analysis arises due to sodium adduction, a problem that increases with molecular weight. Sodium adduction can preclude useful measurements when limited sample sizes prevent off-line cleanup. A novel and generally useful on-line microdialysis technique is described for the rapid (nearly 1-5 min) DNA sample cleanup for ESI-MS. Mass spectra of oligonucleotides of different size and sequence showing no significant sodium adduct peaks were obtained using the on-line microdialysis system with sodium chloride concentrations as high as 250 mM. Signal-to-noise ratios were also greatly enhanced compared to direct infusion of the original samples. By using ammonium acetate as the dialysis buffer, it was also found that the noncovalent association of double-stranded oligonucleotides could be preserved during the microdialysis process, allowing analysis by ESI-MS. 33 refs., 6 figs.
Liu, C.; Wu, Q.; Harms, A.C.; Smith, R.D. [Pacific Northwest National Lab., Richland, WA (United States)] [Pacific Northwest National Lab., Richland, WA (United States)
Controlled-Resonant Surface Tapping-Mode Scanning Probe Electrospray Ionization Mass Spectrometry Imaging
This paper reports on the advancement of a controlled-resonance surface tapping-mode single capillary liquid junction extraction/ESI emitter for mass spectrometry imaging. The basic instrumental setup and the general operation of the system were discussed and optimized performance metrics were presented. The ability to spot sample, lane scan and chemically image in an automated and controlled fashion were demonstrated. Rapid, automated spot sampling was demonstrated for a variety of compound types including the cationic dye basic blue 7, the oligosaccharide cellopentaose, and the protein equine heart cytochrome c. The system was used for lane scanning and chemical imaging of the cationic dye crystal violet in inked lines on glass and for lipid distributions in mouse brain thin tissue sections. Imaging of the lipids in mouse brain tissue under optimized conditions provided a spatial resolution of approximately 35 m based on the ability to distinguish between features observed both in the optical and mass spectral chemical images. The sampling spatial resolution of this system was comparable to the best resolution that has been reported for other types of atmospheric pressure liquid extraction-based surface sampling/ionization techniques used for mass spectrometry imaging.
Lorenz, Matthias [ORNL] [ORNL; Ovchinnikova, Olga S [ORNL] [ORNL; Kertesz, Vilmos [ORNL] [ORNL; Van Berkel, Gary J [ORNL] [ORNL
Membrane-Based Emitter for Coupling Microfluidics with Ultrasensitive Nanoelectrospray Ionization-Mass Spectrometry
An integrated poly(dimethylsiloxane) (PDMS) membrane-based microfluidic emitter for high performance nanoelectrospray ionization-mass spectrometry (nanoESI-MS) has been fabricated and evaluated. The ~100-?m-thick emitter was created by cutting a PDMS membrane that protrudes beyond the bulk substrate. The reduced surface area at the emitter enhances the electric field and reduces wetting of the surface by the electrospray solvent. As such, the emitter provides highly stable electrospray at flow rates as low as 10 nL/min, and is compatible with electrospray solvents containing a large organic component (e.g., 90% methanol). This approach enables facile emitter construction, and provides excellent stability, reproducibility and sensitivity, as well as compatibility with multilayer soft lithography.
Sun, Xuefei; Kelly, Ryan T.; Tang, Keqi; Smith, Richard D.
Molecular Characterization of Organic Aerosols Using Nanospray Desorption/Electrospray Ionization-Mass Spectrometry
Nanospray desorption electrospray ionization (Nano-DESI) combined with high-resolution mass spectrometry (HR/MS) is a promising approach for detailed chemical characterization of atmospheric organic aerosol (OA) collected in laboratory and field experiments. In Nano-DESI analyte is desorbed into a solvent bridge formed between two capillaries and the analysis surface, which enables fast and efficient characterization of OA collected on substrates without special sample preparation. Stable signals achieved using Nano-DESI make it possible to obtain high-quality HR/MS data using only a small amount of material (<10 ng). Furthermore, Nano-DESI enables efficient detection of chemically labile compounds in OA, which is important for understanding chemical aging phenomena.
Roach, Patrick J.; Laskin, Julia; Laskin, Alexander
Picoelectrospray Ionization Mass Spectrometry Using Narrow-bore Chemically Etched Emitters
Electrospray ionization mass spectrometry (ESI-MS) at flow rates below ~10 nL/min has been only sporadically explored due to difficulty in reproducibly fabricating emitters that can operate at lower flow rates. Here we demonstrate narrow orifice chemically etched emitters for stable electrospray at flow rates as low as 400 pL/min. Depending on the analyte concentration, we observe two types of MS signal response as a function of flow rate. At low concentrations, an optimum flow rate is observed slightly above 1 nL/min, while the signal decreases monotonically with decreasing flow rates at higher concentrations. In spite of lower MS signal, the ion utilization efficiency increases exponentially with decreasing flow rate in all cases. No unimolecular response was observed within this flow rate range during the analysis of an equimolar mixture of peptides, indicating that ionization efficiency is an analyte-dependent characteristic in given experimental conditions. While little to no gain in signal-to-noise was achieved at ultralow flow rates for concentration-limited analyses, experiments consuming the same amount of analyte suggest that mass-limited analyses will benefit strongly from the use of low flow rates and avoiding unnecessary sample dilution. By operating under optimal conditions, consumption of just 500 zmol of sample yielded signal-to-noise ratios ~10 for some peptides. These findings have important implications for the analysis of trace biological samples.
Marginean, Ioan; Tang, Keqi; Smith, Richard D.; Kelly, Ryan T.
Electrospray Ionization Mass Spectrometry: From Cluster Ions to Toxic metal Ions in Biology
This dissertation focused on using electrospray ionization mass spectrometry to study cluster ions and toxic metal ions in biology. In Chapter 2, it was shown that primary, secondary and quarternary amines exhibit different clustering characteristics under identical instrument conditions. Carbon chain length also played a role in cluster ion formation. In Chapters 3 and 4, the effects of solvent types/ratios and various instrumental parameters on cluster ion formation were examined. It was found that instrument interface design also plays a critical role in the cluster ion distribution seen in the mass spectrum. In Chapter 5, ESI-MS was used to investigate toxic metal binding to the [Gln{sup 11}]-amyloid {beta}-protein fragment (1-16). Pb and Cd bound stronger than Zn, even in the presence of excess Zn. Hg bound weaker than Zn. There are endless options for future work on cluster ions. Any molecule that is poorly ionized in positive ion mode can potentially show an increase in ionization efficiency if an appropriate anion is used to produce a net negative charge. It is possible that drug protein or drug/DNA complexes can also be stabilized by adding counter-ions. This would preserve the solution characteristics of the complex in the gas phase. Once in the gas phase, CID could determine the drug binding location on the biomolecule. There are many research projects regarding toxic metals in biology that have yet to be investigated or even discovered. This is an area of research with an almost endless future because of the changing dynamics of biological systems. What is deemed safe today may show toxic effects in the future. Evolutionary changes in protein structures may render them more susceptible to toxic metal binding. As the understanding of toxicity evolves, so does the demand for new toxic metal research. New instrumentation designs and software make it possible to perform research that could not be done in the past. What was undetectable yesterday will become routine tomorrow.
Nicholas B. Lentz
Observation of a noncovalent ribonuclease S-protein/S-peptide complex by electrospray ionization mass spectrometry
Electrospray ionization mass spectrometry (ESI-MS) investigations of noncovalently-bound complexes are of great interest because of their relevance to solution biochemistry. ESI-MS is particularly well suited to studies of weak interactions because it is very gentle and it allows studies to be performed under physiological or near-physiological solution conditions. However, it is not yet fully understood which weakly-bound complexes known to exist in solution will be observable by ESI-MS, or what minimum binding strength may be required for ESI-MS observation. Also unclear is whether complexes observed by ESI-MS reflect only species present in the bulk solution, or whether complexes also reflect aggregation in electrospray-generated microdroplets. We address some of these issues by employing ribonuclease S (RNase-S) as a test of the applicability of ESI-MS for analysis of noncovalent complexes. These results show that the ESI mass spectra of R Nase-S can reflect the specificity of binding in solution. 33 refs., 2 figs.
Loo, R.R.O.; Goodlett, D.R.; Smith, R.D.; Loo, J.A. (Pacific Northwest Lab., Richland, WA (United States))
Control of Analyte Electrolysis in Electrospray Ionization Mass Spectrometry Using Repetitively Pulsed High Voltage
Analyte electrolysis using a repetitively pulsed high voltage ion source was investigated and compared to that using a regular, continuously operating direct current high voltage ion source in electrospray ionization mass spectrometry. The extent of analyte electrolysis was explored as a function of the length and frequency of the high voltage pulse using the model compound reserpine in positive ion mode. Using +5 kV as the maximum high voltage amplitude, reserpine was oxidized to its 2, 4, 6 and 8-electron oxidation products when direct current high voltage was employed. In contrast, when using a pulsed high voltage, oxidation of reserpine was eliminated by employing the appropriate high voltage pulse length and frequency. This effect was caused by inefficient mass transport of the analyte to the electrode surface during the duration of the high voltage pulse and the subsequent relaxation of the emitter electrode/ electrolyte interface during the time period when the high voltage was turned off. This mode of ESI source operation allows for analyte electrolysis to be quickly and simply switched on or off electronically via a change in voltage pulse variables.
Kertesz, Vilmos [ORNL; Van Berkel, Gary J [ORNL
The Effect of Solvent on the Analysis of Secondary Organic Aerosol Using Electrospray Ionization Mass Spectrometry
Solvent-analyte reactions in organic aerosol (OA) extracts prepared for analysis by electrospray ionization mass spectrometry (ESI-MS) were examined. Secondary organic aerosol (SOA) produced by ozonation of d-limonene as well as several test organic chemicals with functional groups typical for OA constituents were dissolved and stored in methanol, d3-methanol, acetonitrile, and d3-acetonitrile to investigate the extent and relative rates of reactions between analyte and solvent. High resolution ESI-MS showed that reactions of carbonyls with methanol produce significant amounts of hemiacetals and acetals on time scales ranging from several minutes to several days, with the reaction rates increasing in acidified solutions. Carboxylic acid groups were observed to react with methanol resulting in the formation of esters. In contrast, acetonitrile extracts showed no evidence of reactions with analyte molecules, suggesting that acetonitrile is the preferred solvent for SOA extraction. The use of solvent-analyte reactivity as an analytical chemistry tool for the improved characterization of functional groups in complex organic mixtures was also demonstrated. Direct comparison between ESI mass spectra of the same SOA samples extracted in reactive (methanol) versus non-reactive (acetonitrile) solvents was used to estimate the relative fractions of ketones (?38%), aldehydes (?6%), and carboxylic acids (?55%) in d-limonene SOA.
Bateman, Adam P.; Walser, Maggie L.; Dessiaterik, Yury; Laskin, Julia; Laskin, Alexander; Nizkorodov, Serguei
Chemical Analysis of Complex Organic Mixtures Using Reactive Nanospray Desorption Electrospray Ionization Mass Spectrometry
Reactive nanospray desorption electrospray ionization (nano-DESI) combined with high-resolution mass spectrometry was utilized for the analysis of secondary organic aerosol produced through ozonolysis of limonene (LSOA). Previous studies showed that LSOA constituents are multifunctional compounds containing aldehyde and ketone groups. In this study, we used the selectivity of the Girard T (GT) reagent towards carbonyl compounds to examine the utility of reactive nano-DESI for the analysis of complex organic mixtures. In these experiments, 1-100 {micro}M GT solution was used as a working solvent for reactive nano-DESI analysis. Abundant products of a single addition of GT to LSOA constituents were observed at GT concentrations in excess of 10 {micro}M. We found that LSOA compounds with 18-20 carbon atoms (dimers) and 27-30 carbon atoms (trimers) react with GT through a simple addition reaction resulting in formation of the carbinolamine derivative. In contrast, reactions of GT with monomeric species result in formation of both the carbinolamine and the hydrazone derivatives. In addition, several monomers did not react with GT on the timescale of our experiment. These molecules were characterized by relatively high values of the double bond equivalent (DBE) and low oxygen content. Furthermore, because addition of a charged GT tag to a neutral molecule eliminates the discrimination against the low proton affinity compounds in the ionization process, reactive nano-DESI analysis enables quantification of individual compounds in the complex mixture. For example, we were able to estimate for the first time the amounts of dimers and trimers in the LSOA mixture. Specifically, we found that the most abundant LSOA dimer was detected at ca. 0.5 pg level and the total amount of dimers and trimers in the analyzed sample was just around 11 pg. Our results indicate that reactive nano-DESI is a valuable approach for examining the presence of specific functional groups and quantification of compounds possessing these groups in complex mixtures.
Laskin, Julia; Eckert, Peter A.; Roach, Patrick J.; Heath, Brandi S.; Nizkorodov, Sergey A.; Laskin, Alexander
Laser vaporization/ionization interface for coupling microscale separation techniques with mass spectrometry
The present invention provides a laser-induced vaporization and ionization interface for directly coupling microscale separation processes to a mass spectrometer. Vaporization and ionization of the separated analytes are facilitated by the addition of a light-absorbing component to the separation buffer or solvent. 8 figs.
Yeung, E.S.; Chang, Y.C.
Observation of the noncovalent quaternary associations of proteins by electrospray ionization mass spectrometry
The noncovalent tetrameric active forms of avidin, concanavalin A (Con A), and adult human hemoglobin (HbA[sub 0]) can be observed intact in the gas phase by electrospray ionization mass spectrometry (ESI-MS). The atmosphere-vacuum ESI interface conditions strongly influence the retention of these weak noncovalent solution associations into the gas phase, as well as the average extent of charging for the subunits upon dissociation. The known solution pH dependence of the dimer-tetramer equilibrium of Con A was observed by ESI-MS, and the intact heterodimeric and -tetrameric active forms of adult human HbA[sub 0], ([alpha][beta]) and ([alpha][beta])[sub 2], with the prosthetic heme groups could also be characterized by ESI-MS. Under harsher interface conditions a species corresponding to a trimer was observed for each of the proteins, a species not known to be formed under physiological conditions. Differences in the relative stabilities of these tetrameric proteins, formed from the known solution structures, are also qualitatively consistent with the gas-phase stability observed with ESI-MS by adjusting the atmosphere-vacuum interface conditions. The hemoglobin tetramer was found to be less stable in the gas phase than either the Con A or avidin tetramer, consistent with solution dissociation constants. 21 refs., 14 figs.
Light-Wahl, K.J.; Schwartz, B.L.; Smith, R.D. (Pacific Northwest Lab., Richland, WA (United States))
Imaging Nicotine in Rat Brain Tissue by Use of Nanospray Desorption Electrospray Ionization Mass Spectrometry
Imaging mass spectrometry offers simultaneous detection of drugs, drug metabolites and endogenous substances in a single experiment. This is important when evaluating effects of a drug on a complex organ system such as the brain, where there is a need to understand how regional drug distribution impacts function. Nicotine is an addictive drug and its action in the brain is of high interest. Here we use nanospray desorption electrospray ionization, nano-DESI, imaging to discover the localization of nicotine in rat brain tissue after in vivo administration of nicotine. Nano-DESI is a new ambient technique that enables spatially-resolved analysis of tissue samples without special sample pretreatment. We demonstrate high sensitivity of nano-DESI imaging that enables detection of only 0.7 fmole nicotine per pixel in the complex brain matrix. Furthermore, by adding deuterated nicotine to the solvent, we examined how matrix effects, ion suppression, and normalization affect the observed nicotine distribution. Finally, we provide preliminary results suggesting that nicotine localizes to the hippocampal substructure called dentate gyrus.
Lanekoff, Ingela T.; Thomas, Mathew; Carson, James P.; Smith, Jordan N.; Timchalk, Charles; Laskin, Julia
Metabolic Profiling Directly from the Petri Dish Using Nanospray Desorption Electrospray Ionization Imaging Mass Spectrometry
Understanding molecular interaction pathways in complex biological systems constitutes a treasure trove of knowledge that might facilitate the specific, chemical manipulation of the countless microbiological systems that occur throughout our world. However, there is a lack of methodologies that allow the direct investigation of chemical gradients and interactions in living biological systems, in real time. Here, we report the use of nanospray desorption electrospray ionization (nanoDESI) imaging mass spectrometry for in vivo metabolic profiling of living bacterial colonies directly from the Petri dish with absolutely no sample preparation needed. Using this technique, we investigated single colonies of Shewanella oneidensis MR-1, Bacillus subtilis 3610, and Streptomyces coelicolor A3(2) as well as a mixed biofilm of S. oneidensis MR-1 and B. subtilis 3610. Data from B. subtilis 3610 and S. coelicolor A3(2) provided a means of validation for the method while data from S. oneidensis MR-1 and the mixed biofilm showed a wide range of compounds that this bacterium uses for the dissimilatory reduction of extracellular metal oxides, including riboflavin, iron-bound heme and heme biosynthetic intermediates, and the siderophore putrebactin.
Watrous, Jeramie D.; Roach, Patrick J.; Heath, Brandi S.; Alexandrov, Theodore; Laskin, Julia; Dorrestein, Pieter C.
A study of the tropospheric oxidation of volatile organic compounds using chemical ionization mass spectrometry
The mechanisms and kinetics of reactions important to the troposphere have been investigated using a high pressure, turbulent, discharge-flow technique coupled to a chemical ionization mass spectrometer. The ability to ...
Broekhuizen, Keith Edward, 1974-
Very high resolution saturation spectroscopy of lutetium isotopes via c-w single-frequency laser resonance ionization mass spectrometry
In this paper, we discuss the use of Resonance Ionization Mass Spectrometry (RIMS) to perform isotopically selective saturation spectroscopy of lutetium isotopes. Utilizing this technique, it is shown that accurate measurements of the relative frequencies of hyperfine (HF) components for different isotopes easily can be made without the need for an isotopically enriched sample. The precision with which the HF splitting constants can be determined is estimated to be approx.5 times greater than in previous work.
Fearey, B.L.; Parent, D.C.; Keller, R.A.; Miller, C.M.
Fully Automated Laser Ablation Liquid Capture Sample Analysis using NanoElectrospray Ionization Mass Spectrometry
RATIONALE: Laser ablation provides for the possibility of sampling a large variety of surfaces with high spatial resolution. This type of sampling when employed in conjunction with liquid capture followed by nanoelectrospray ionization provides the opportunity for sensitive and prolonged interrogation of samples by mass spectrometry as well as the ability to analyze surfaces not amenable to direct liquid extraction. METHODS: A fully automated, reflection geometry, laser ablation liquid capture spot sampling system was achieved by incorporating appropriate laser fiber optics and a focusing lens into a commercially available, liquid extraction surface analysis (LESA ) ready Advion TriVersa NanoMate system. RESULTS: Under optimized conditions about 10% of laser ablated material could be captured in a droplet positioned vertically over the ablation region using the NanoMate robot controlled pipette. The sampling spot size area with this laser ablation liquid capture surface analysis (LA/LCSA) mode of operation (typically about 120 m x 160 m) was approximately 50 times smaller than that achievable by direct liquid extraction using LESA (ca. 1 mm diameter liquid extraction spot). The set-up was successfully applied for the analysis of ink on glass and paper as well as the endogenous components in Alstroemeria Yellow King flower petals. In a second mode of operation with a comparable sampling spot size, termed laser ablation/LESA , the laser system was used to drill through, penetrate, or otherwise expose material beneath a solvent resistant surface. Once drilled, LESA was effective in sampling soluble material exposed at that location on the surface. CONCLUSIONS: Incorporating the capability for different laser ablation liquid capture spot sampling modes of operation into a LESA ready Advion TriVersa NanoMate enhanced the spot sampling spatial resolution of this device and broadened the surface types amenable to analysis to include absorbent and solvent resistant materials.
Lorenz, Matthias [ORNL] [ORNL; Ovchinnikova, Olga S [ORNL] [ORNL; Van Berkel, Gary J [ORNL] [ORNL
Chemical Characterization of Crude Petroleum Using Nanospray Desorption Electrospray Ionization Coupled with High-Resolution Mass Spectrometry
Nanospray desorption electrospray ionization (nano-DESI) combined with high-resolution mass spectrometry was used for the first time for the analysis of liquid petroleum crude oil samples. The analysis was performed in both positive and negative ionization modes using three solvents one of which (acetonitrile/toluene mixture) is commonly used in petroleomics studies while two other polar solvents (acetonitrile/water and methanol/water mixtures) are generally not compatible with petroleum characterization using mass spectrometry. The results demonstrate that nano-DESI analysis efficiently ionizes petroleum constituents soluble in a particular solvent. When acetonitrile/toluene is used as a solvent, nano-DESI generates electrospray-like spectra. In contrast, strikingly different spectra were obtained using acetonitrile/water and methanol/water. Comparison with the literature data indicates that these solvents selectively extract water-soluble constituents of the crude oil. Water-soluble compounds are predominantly observed as sodium adducts in nano-DESI spectra indicating that addition of sodium to the solvent may be a viable approach for efficient ionization of water-soluble crude oil constituents. Nano-DESI enables rapid screening of different classes of compounds in crude oil samples using solvents that are rarely used for petroleum characterization.
Eckert, Peter A.; Roach, Patrick J.; Laskin, Alexander; Laskin, Julia
Determination of naphthenic acids in California crudes and refinery waste waters by fluoride ion chemical ionization mass spectrometry
A method based on negative ion chemical ionization mass spectrometry using fluoride (F/sup -/) ions produced from NF/sub 3/ reagent gas has been applied to the analysis of naphthenic acids in California crude oils and refinery waste waters. Since complex mixtures of naphthenic acids cannot be separated into individual components, only the determination of relative distribution of acids classified by the hydrogen deficiency was possible. The identities and relative distribution of paraffinic and mono-, di-, tri, and higher polycyclic acids were obtained from the intensities of the carboxylate (RCOO/sup -/) ions.
Dzidic, I.; Somerville, A.C.; Raia, J.C.; Hart, H.V.
Applications of High-Resolution Electrospray Ionization Mass...
High-Resolution Electrospray Ionization Mass Spectrometry to Measurements of Average Oxygen to Carbon Ratios in Applications of High-Resolution Electrospray Ionization Mass...
Combining Laser Ablation/Liquid Phase Collection Surface Sampling and High-Performance Liquid Chromatography Electrospray Ionization Mass Spectrometry
This paper describes the coupling of ambient pressure transmission geometry laser ablation with a liquid phase sample collection method for surface sampling and ionization with subsequent mass spectral analysis. A commercially available autosampler was adapted to produce a liquid droplet at the end of the syringe injection needle while in close proximity to the surface to collect the sample plume produced by laser ablation. The sample collection was followed by either flow injection or a high performance liquid chromatography (HPLC) separation of the extracted components and detection with electrospray ionization mass spectrometry (ESI-MS). To illustrate the analytical utility of this coupling, thin films of a commercial ink sample containing rhodamine 6G and of mixed isobaric rhodamine B and 6G dyes on glass microscope slides were analyzed. The flow injection and HPLC/ESI-MS analysis revealed successful laser ablation, capture and, with HPLC, the separation of the two compounds. The ablated circular area was about 70 m in diameter for these experiments. The spatial sampling resolution afforded by the laser ablation, as well as the ability to use sample processing methods like HPLC between the sample collection and ionization steps, makes this combined surface sampling/ionization technique a highly versatile analytical tool.
Ovchinnikova, Olga S [ORNL; Kertesz, Vilmos [ORNL; Van Berkel, Gary J [ORNL
Using electrospray ionization FTICR mass spectrometry to study competitive binding of inhibitors to carbonic anhydrase
We report a method based on mass spectrometry for the characterization of noncovalent complexes of proteins with mixtures of ligands; this method is relevant to the study of drug leads and may be useful in screening libraries for tight-binding compounds. This study describes the competitive binding of inhibitors derived from para-substituted benzenesulfonamides to bovine carbonic anhydrase II (BCAII, EC 22.214.171.124) using this technique. Relative binding constants and structural information for a mixture of inhibitors can be obtained in a single experiment using ESI-FTICR-MS. The work demonstrates that ESI-MS has significant potential for measuring relative binding affinities and characterizing the structures of ligands associated noncovalently to proteins. We have detected noncovalent complexes in the gas phase for ligands having values of K{sub b} as low as 1.7 x 10{sup 6} M{sup -1} in solution. The technique also allowed identification of tightbinding ligands from small libraries. The structures of inhibitors having similar masses can be identified by the high-resolution and multistep dissociation mass spectrometry of which FTICR is uniquely capable. This range of capabilities for ESI-FTICR-MS should be widely useful in medicinal chemistry. 22 refs., 2 figs.
Cheng, X.; Chen, R.; Bruce, J.E.; Schwartz, B.L.; Anderson, G.A.; Hofstadler, S.A.; Gale, D.C.; Smith, R.D. [Pacific Northwest Lab., Richland, WA (United States); Gao, J.; Sigal, G.B.; Mammen, M.; Whitesides, G.M. [Harvard Univ., Cambridge, MA (United States)
Observation of a small oligonucleotide duplex by electrospray ionization mass spectrometry
Electrospray ionization (ESI) has been demonstrated to be a soft ionization technique, allowing accurate molecular weight determination for biopolymers due to gas-phase multiple charging. Recent results have demonstrated that noncovalent associations can be preserved upon transfer into the gas phase with ESI, providing a new approach to the determination of both structurally-specific and nonspecific noncovalent associations in solution. The mass spectrometric experimental conditions necessary to preserve such noncovalent associations, and the physical constraints upon such, have yet to be elucidated, although it is clear that gentle interface conditions minimizing internal excitation of noncovalent complexes are helpful. Base-paired oligonucleotide hybridization constitutes one of the most important and thoroughly studied noncovalent associations of biopolymers. Initial attempts to observe duplex oligonucleotides resulted in detection of only the monomeric constituents. Since then, the authors have developed interface conditions that are more gentle and yet still provide sufficient molecular ion desolvation to preserve such associations using new instrumentation with a greatly extended m/z range. In this communication, the authors report the successful ionization of duplex oligonucleotides and the conditions necessary for detection by negative ion ESI-MS. 6 refs., 1 fig.
Light-Wahl, K.J.; Springer, D.L.; Winger, B.E.; Edmonds, C.G.; Thrall, B.D.; Smith, R.D. (Pacific Northwest Lab., Richland, WA (United States)); Camp, D.G. II (Eastern Oregon State College, La Grande (United States))
ablation mass spectrometry: Topics by E-print Network
and laser ablation electrospray ionization mass Chemistry Websites Summary: -mass spectrometry (DESI-MS) and laser ablation electrospray ionization-MS (LAESI-MS) were used to...
Laser desorption/ionization mass spectrometry for direct profiling and imaging of small molecules from raw biological materials
Matrix-assisted laser desorption/ionization(MALDI) mass spectrometry(MS) has been widely used for analysis of biological molecules, especially macromolecules such as proteins. However, MALDI MS has a problem in small molecule (less than 1 kDa) analysis because of the signal saturation by organic matrixes in the low mass region. In imaging MS (IMS), inhomogeneous surface formation due to the co-crystallization process by organic MALDI matrixes limits the spatial resolution of the mass spectral image. Therefore, to make laser desorption/ionization (LDI) MS more suitable for mass spectral profiling and imaging of small molecules directly from raw biological tissues, LDI MS protocols with various alternative assisting materials were developed and applied to many biological systems of interest. Colloidal graphite was used as a matrix for IMS of small molecules for the first time and methodologies for analyses of small metabolites in rat brain tissues, fruits, and plant tissues were developed. With rat brain tissues, the signal enhancement for cerebroside species by colloidal graphite was observed and images of cerebrosides were successfully generated by IMS. In addition, separation of isobaric lipid ions was performed by imaging tandem MS. Directly from Arabidopsis flowers, flavonoids were successfully profiled and heterogeneous distribution of flavonoids in petals was observed for the first time by graphite-assisted LDI(GALDI) IMS.
Cha, Sangwon
Time-Resolved Molecular Characterization of Limonene/Ozone Aerosol using High-Resolution Electrospray Ionization Mass Spectrometry
Molecular composition of limonene/O3 secondary organic aerosol (SOA) was investigated using high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) as a function of reaction time. SOA was generated by ozonation of D-limonene in a reaction chamber and sampled at different time intervals using a cascade impactor. The SOA samples were extracted into acetonitrile and analyzed using a HR-ESI-MS instrument with a resolving power of 100,000 (m/?m). The resulting mass spectra provided detailed information about the extent of oxidation inferred from the O:C ratios, double bond equivalency (DBE) factors, and aromaticity indexes (AI) in hundreds of identified individual SOA species.
Bateman, Adam P.; Nizkorodov, Serguei; Laskin, Julia; Laskin, Alexander
Characterization of nonpolar lipids and steroids by using laser-induced acoustic desorption/chemical ionization, atmospheric pressure chemical ionization, and electrospray ionization mass spectrometry
Laser-induced acoustic desorption (LIAD) combined with ClMn(H{sub 2}O){sup +} chemical ionization (CI) was tested for the analysis of nonpolar lipids and selected steroids in a Fourier-transform ion cyclotron resonance mass spectrometer (FT-ICR). The nonpolar lipids studied, cholesterol, 5?-cholestane, cholesta-3,5-diene, squalene, and ?-carotene, were found to solely form the desired water replacement product (adduct-H{sub 2}O) upon reaction with the ClMn(H{sub 2}O){sup +} ions. The steroids, androsterone, dehydroepiandrosterone (DHEA), estrone, estradiol, and estriol, also form abundant adduct-H{sub 2}O ions, but less abundant adduct-2H{sub 2}O ions were also observed. Neither (+)APCI nor (+)ESI can ionize the saturated hydrocarbon lipid, cholestane. APCI successfully ionizes the unsaturated hydrocarbon lipids to form exclusively the intact protonated analytes. However, it causes extensive fragmentation for cholesterol and the steroids. The worst case is cholesterol that does not produce any stable protonated molecules. On the other hand, ESI cannot ionize any of the hydrocarbon analytes, saturated or unsaturated. However, ESI can be used to protonate the oxygen-containing analytes with substantially less fragmentation than for APCI in all cases except for cholesterol and estrone. In conclusion, LIAD/ClMn(H{sub 2}O){sup +} chemical ionization is superior over APCI and ESI for the mass spectrometric characterization of underivatized nonpolar lipids and steroids.
Jin, Z.; Daiya, S.; Kentt�maa, Hilkka I.
High-Resolution Electrospray Ionization Mass Spectrometry Analysis of Water- Soluble Organic Aerosols Collected with a Particle into Liquid Sampler
This work demonstrates the utility of a particle-into-liquid sampler (PILS) a technique traditionally used for identification of inorganic ions present in ambient or laboratory aerosols for the analysis of water soluble organic aerosol (OA) using high resolution electrospray ionization mass spectrometry (HR ESI-MS). Secondary organic aerosol (SOA) was produced from 0.5 ppm mixing ratios of limonene and ozone in a 5 m3 Teflon chamber. SOA was collected simultaneously using a traditional filter sampler and a PILS. The filter samples were later extracted with either water or acetonitrile, while the aqueous PILS samples were analyzed directly. In terms of peak intensities, types of detectable compounds, average O:C ratios, and organic mass to organic carbon ratios, the resulting high resolution mass spectra were essentially identical for the PILS and filter based samples. SOA compounds extracted from both filter/acetonitrile extraction and PILS/water extraction accounted for >95% of the total ion current in ESI mass spectra. This similarity was attributed to high solubility of limonene SOA in water. In contrast, significant differences in detected ions and peak abundances were observed for pine needle biomass burning organic aerosol (BBOA) collected with PILS and filter sampling. The water soluble fraction of BBOA is considerably smaller than for SOA, and a number of unique peaks were detectable only by the filter/acetonitrile method. The combination of PILS collection with HR-ESI-MS analysis offers a new approach for molecular analysis of the water-soluble organic fraction in biogenic SOA, aged photochemical smog, and BBOA.
Improving liquid chromatography-mass spectrometry sensitivity using a subambient pressure ionization with nanoelectrospray (SPIN) interface
In this work the Subambient Pressure Ionization with Nanoelectrospray (SPIN) ion source and interface which operates at ~15-30 Torr is demonstrated to be compatible with gradient reversed-phase liquid chromatography-MS applications, exemplified here with the analysis of complex samples (a protein tryptic digest and a whole cell lysate). A low liquid chromatographic flow rate (100-400 nL/min) allowed stable electrospray to be established while avoiding electrical breakdown. Efforts to increase the operating pressure of the SPIN source relative to previously reported designs prevented solvent freezing and enhanced charged cluster/droplet desolvation. A 5-12-fold improvement in sensitivity relative to a conventional atmospheric pressure nanoelectrospray ionization (ESI) source was obtained for detected peptides.
Tang, Keqi; Page, Jason S.; Marginean, Ioan; Kelly, Ryan T.; Smith, Richard D.
Isotopically selective, Doppler-free, saturation spectroscopy of lutetium isotopes via resonance ionization mass spectrometry
A new technique utilizing RIMS to obtain very high resolution atomic spectra with isotopic selectivity has been demonstrated. This technique allows the precise determination of HF splitting constants, limited only by the transition's natural linewidth. In addition, it is also feasible with this technique to accurately determine atomic isotope shifts. The exact determination of HF component line positions provides data for isotopically selective ionization which, in turn, will increase RIMS' dynamic range. Future work includes the incorporation of a /open quotes/vibrating/close quotes/ mirror and the study of rarer isotopes, i.e., /sup 174/Lu, /sup 173/Lu, /sup 172/Lu, /sup 171/Lu, and possibly, /sup 170/Lu. 13 refs., 3 figs.
Size-selected 2, 5, and 10 nm gold nanoparticles for laser desorption/ionization mass spectrometry
, as subtle changes in the solution environment can result in subsequent changes in the mass spectra. A thorough evaluation of the parameters that affect desorption/ionization of peptides is presented here, and these parameters include: (i) AuNP-to...
Stumpo, Katherine Anne
Gas Chromatography -Mass Spectrometry
GCMS - 1 Gas Chromatography - Mass Spectrometry GC-MS ANALYSIS OF ETHANOL AND BENZENE IN GASOLINE Last updated: June 17, 2014 #12;GCMS - 2 Gas Chromatography - Mass Spectrometry GC-MS ANALYSIS). The goal of this experiment is to separate the components in a sample of gasoline using Gas Chromatography
Nizkorodov, Sergey
Facilities: NHMFL 9.4 Tesla Fourier Transform Ion Cyclotron Resonance Mass Spectrometer Citation: Atmospheric Pressure Laser-Induced Acoustic Desorption Chemical Ionization Mass Spectrometry
. Rodgers, & Alan G. Marshall, Analytical Chemistry 84, 7131-7137 (2012). Figure 1. Schematic diagram hydrocarbons (the primary components of gasoline) are difficult to analyze by mass spectrometry, because
Weston, Ken
Applications of High-Resolution Electrospray Ionization Mass Spectrometry to Measurements of Average Oxygen to Carbon Ratios in Secondary Organic Aerosols
The applicability of high resolution electrospray ionization mass spectrometry (HR ESI-MS) to measurements of the average oxygen to carbon ratio (O/C) in organic aerosols was investigated. Solutions with known average O/C containing up to 10 standard compounds representative of secondary organic aerosol (SOA) were analyzed and corresponding electrospray ionization efficiencies were quantified. The assumption of equal ionization efficiency commonly used in estimating O/C ratios of organic aerosols was found to be reasonably accurate. We found that the accuracy of the measured O/C ratios increases by averaging the values obtained from both (+) and (-) modes. A correlation was found between the ratio of the ionization efficiencies in the positive and negative ESI modes with the octanol-water partition constant, and more importantly, with the compound's O/C. To demonstrate the utility of this correlation for estimating average O/C values of unknown mixtures, we analyzed the ESI (+) and ESI (-) data for SOA produced by oxidation of limonene and isoprene and compared to online O/C measurements using an aerosol mass spectrometer (AMS). This work demonstrates that the accuracy of the HR ESI-MS methods is comparable to that of the AMS, with the added benefit of molecular identification of the aerosol constituents.
Bateman, Adam P.; Laskin, Julia; Laskin, Alexander; Nizkorodov, Sergey
ambient mass spectrometry: Topics by E-print Network
and Applications of Liquid Sample Desorption Electrospray Ionization Mass Spectrometry (DESI-MS). Open Access Theses and Dissertations Summary: ?? This dissertation...
aerosol mass spectrometry: Topics by E-print Network
analysis of aerosol organic nitrates with electron ionization high-resolution mass spectrometry MIT - DSpace Summary: Four hydroxynitrates (R(OH)R'ONO2) representative of...
Liquid Sampling-Atmospheric Pressure Glow Discharge (LS-APGD) Ionization Source for Elemental Mass Spectrometry: Preliminary Parametric Evaluation and Figures of Merit
A new, low power ionization source for the elemental analysis of aqueous solutions has recently been described. The liquid sampling-atmospheric pressure glow discharge (LS-APGD) source operates at relatively low currents (<20 mA) and solution flow rates (<50 ?L min-1), yielding a relatively simple alternative for atomic mass spectrometry applications. The LS-APGD has been interfaced to what is otherwise an organic, LC-MS mass analyzer, the Thermo Scientific Exactive Orbitrap without any modifications; other than removing the electrospray ionization (ESI) source supplied with that instrument. A glow discharge is initiated between the surface of the test solution exiting a glass capillary and a metallic counter electrode mounted at a 90� angle and separated by a distance of ~5 mm. As with any plasma-based ionization source, there are key discharge operation and ion sampling parameters that affect the intensity and composition of the derived mass spectra; including signal-to-background ratios. We describe here a preliminary parametric evaluation of the roles of discharge current, solution flow rate, argon sheath gas flow rate, and ion sampling distance as they apply on this mass analyzer system. A cursive evaluation of potential matrix effects due to the presence of easily ionized elements (EIEs) indicate that sodium concentrations of up to 500 ?g mL-1 generally cause suppressions of less than 50%, dependant upon the analyte species. Based on the results of this series of studies, preliminary limits of detection (LOD) have been established through the generation of calibration functions. Whilst solution-based concentrations LOD levels of 0.02 � 2 ?g mL-1 3 are not impressive on the surface, the fact that they are determined via discrete 5 ?L injections leads to mass-based detection limits at picogram to singlenanogram levels. The overhead costs associated with source operation (10 W d.c. power, solution flow rates of <50 ?L min-1, and gas flow rates <10 mL min-1) are very attractive. While further optimization in the source design is suggested here, it is believed that the LS-APGD ion source may present a practical alternative to inductively-coupled plasma (ICP) sources typically employed in elemental mass spectrometry.
Quarles, C. Derrick; Carado, Anthony J.; Barinaga, Charles J.; Koppenaal, David W.; Marcus, R. Kenneth
Combined Atomic Force Microscope-Based Topographical Imaging and Nanometer Scale Resolved Proximal Probe Thermal Desorption/Electrospray Ionization-Mass Spectrometry
Nanometer scale proximal probe thermal desorption/electrospray ionization mass spectrometry (TD/ESI-MS) was demonstrated for molecular surface sampling of caffeine from a thin film using a 30 nm diameter nano-thermal analysis (nano-TA) probe tip in an atomic force microscope (AFM) coupled via a vapor transfer line and ESI interface to a MS detection platform. Using a probe temperature of 350 C and a spot sampling time of 30 s, conical desorption craters 250 nm in diameter and 100 nm deep were created as shown through subsequent topographical imaging of the surface within the same system. Automated sampling of a 5 x 2 array of spots, with 2 m spacing between spots, and real time selective detection of the desorbed caffeine using tandem mass spectrometry was also demonstrated. Estimated from the crater volume (~2x106 nm3), only about 10 amol (2 fg) of caffeine was liberated from each thermal desorption crater in the thin film. These results illustrate a relatively simple experimental setup and means to acquire in automated fashion sub-micrometer scale spatial sampling resolution and mass spectral detection of materials amenable to TD. The ability to achieve MS-based chemical imaging with 250 nm scale spatial resolution with this system is anticipated.
Ovchinnikova, Olga S [ORNL; Nikiforov, Maxim [ORNL; Bradshaw, James A [ORNL; Jesse, Stephen [ORNL; Van Berkel, Gary J [ORNL
Molecular Characterization of Organosulfates in Organic Aerosols from Shanghai and Los Angeles Urban Areas by Nanospray-Desorption Electrospray Ionization High-Resolution Mass Spectrometry
Aerosol samples collected in the urban areas of Shanghai and Los Angeles were analyzed by nanospray-desorption electrospray ionization mass spectrometry (nano-DESI MS) with high mass resolution (m/?m=100,000). Solvent mixtures of acetonitrile/water and acetonitrile/toluene were used to extract and ionize polar and non-polar compounds, respectively. A diverse mixture of oxygenated hydrocarbons, organosulfates, organonitrates, and organics with reduced nitrogen were detected in the Los Angeles sample. Majority of the organics in the Shanghai sample were detected as organosulfates. The dominant organosulfates in the two samples have distinctly different molecular characteristics. Specifically, organosulfates in the Los Angeles sample were dominated by isoprene- or monoterpene-derived products, while organosulfates of yet unknown origin in the Shanghai sample had distinctive characteristics of long aliphatic carbon chains and low degree of oxidation and unsaturation. The use of acetonitrile/toluene solvent facilitated identification of this type of organosulfates, suggesting they could be missed in previous studies relying on sample extraction using common polar solvents. The high molecular weight and low degree of unsaturation and oxidization of the organosulfates detected in the Shanghai sample suggest that they may act as surfactants, and plausibly affect the surface tension and hygroscopicity of the atmospheric particulate matter. We propose that direct esterification of carbonyl or hydroxyl compounds by sulfates or sulfuric acid in liquid phase could be the formation pathway of these special organosulfates. Long-chain alkanes from vehicle emissions might be their precursors.
Tao, Shikang; Lu, Xiaohui; Levac, Nicole A.; Bateman, Adam P.; Nguyen, Tran B.; Bones, David L.; Nizkorodov, Sergey; Laskin, Julia; Laskin, Alexander; Yang, Xin
reported work in high energy mass spectrometry-two in 1938,importance of high energy mass spectrometry was demonstrated
Alvarez, L.W.
Applications of High-Resolution Electrospray Ionization Mass Spectrometry to Measurements of Average Oxygen to Carbon Ratios
, California 92617, United States Chemical and Materials Sciences Division and � Environmental Molecular. A correlation was found between the ratio of the ionization efficiencies in the positive (+) and negative identification of the aerosol constituents. INTRODUCTION Due to the molecular complexity inherent to secondary
Poly(3,4-ethylenedioxypyrrole) Modified Emitter Electrode for Substitution of Homogeneous Redox Buffer Agent Hydroquinone in Electrospray Ionization Mass Spectrometry
The electrolysis inherent to the operation of the electrospray ionization (ESI) source used with mass spectrometry (MS) is a well-known attendant effect of generating unipolar spray droplets and may affect the analysis of the analyte of interest. Undesirable electrolysis of an analyte may be prevented by limiting the emitter electrode current and/or the mass transport characteristics of the system. However, these ways to avoid analyte electrolysis may not be applcable in all ESI-MS experiments. For example, in the case of specific nanospray systems (e.g. the wire-in-a-capillary bulk-loaded or chip-based tip-loaded nanospray configurations), the solution flow rate is fixed in the 50-500 nL/min range and the electrode surface to volume ratio is large presenting a very effcient analyte to electrode mass transport configuration. In these situations, control over the interfacial potential of the working electrode via homogeneous or traditional heterogeneous (sacrificial metal) redox buffering is a possible way to prevent analyte electrolysis. However, byproducts of these redox buffering approaches can appear in the mass spectra and/or they can chemically alter the analyte. For example, the main reason for using hydroquinone as a homogeneous redox buffer, in addition to its relatively low oxidation potential, is that neither the original compound nor its oxidation product benzoquinone can be detected directly by ESI-MS. However, benzoquinone can alter analytes with thiol functional groups by reacting with those groups via a 1,4-Michael addition.
Peintler-Krivan, Emese [ORNL; Van Berkel, Gary J [ORNL; Kertesz, Vilmos [ORNL
System and method of infrared matrix-assisted laser desorption/ionization mass spectrometry in polyacrylamide gels
A system and method for desorption and ionization of analytes in an ablation medium. In one embodiment, the method includes the steps of preparing a sample having analytes in a medium including at least one component, freezing the sample at a sufficiently low temperature so that at least part of the sample has a phase transition, and irradiating the frozen sample with short-pulse radiation to cause medium ablation and desorption and ionization of the analytes. The method further includes the steps of selecting a resonant vibrational mode of at least one component of the medium and selecting an energy source tuned to emit radiation substantially at the wavelength of the selected resonant vibrational mode. The medium is an electrophoresis medium having polyacrylamide. In one embodiment, the energy source is a laser, where the laser can be a free electron laser tunable to generate short-pulse radiation. Alternatively, the laser can be a solid state laser tunable to generate short-pulse radiation. The laser can emit light at various ranges of wavelength.
Haglund Jr., Richard F.; Ermer, David R.; Baltz-Knorr, Michelle Lee
Effusive molecular beam-sampled Knudsen flow reactor coupled to vacuum ultraviolet single photon ionization mass spectrometry using an external free radical source
A new apparatus using vacuum ultraviolet single photon ionization mass spectrometry (VUV SPIMS) of an effusive molecular beam emanating from a Knudsen flow reactor is described. It was designed to study free radical-molecule kinetics over a significant temperature range (300�630 K). Its salient features are: (1) external free radical source, (2) counterpropagating molecular beam and diffuse VUV photon beam meeting in a crossed-beam ion source of a quadrupole mass spectrometer with perpendicular ion extraction, (3) analog detection of the photocurrent of the free radical molecular cation, and (4) possibility of detecting both free radicals and closed shell species in the same apparatus and under identical reaction conditions owing to the presence of photoelectrons generated by the photoelectric effect of the used VUV-photons. The measured thermal molecular beam-to-background ratio was 6.35 � 0.39 for Ar and 10.86 � 1.59 for i-C{sub 4}H{sub 10} at 300 K, a factor of 2.52 and 1.50 smaller, respectively, than predicted from basic gas-dynamic considerations. Operating parameters as well as the performance of key elements of the instrument are presented and discussed. Coupled to an external free radical source a steady-state specific exit flow of 1.6 � 10{sup 11} and 5.0 � 10{sup 11} molecule s{sup ?1} cm{sup ?3} of C{sub 2}H{sub 5}{sup �} (ethyl) and t-C{sub 4}H{sub 9}{sup �} (t-butyl) free radicals have been detected using VUV SPIMS at their molecular ion m/z 29 and 57, respectively, at 300 K.
Leplat, N.; Rossi, M. J. [Laboratory of Atmospheric Chemistry (LAC), Paul Scherrer Institute (PSI), CH-5232 Villigen PSI (Switzerland)] [Laboratory of Atmospheric Chemistry (LAC), Paul Scherrer Institute (PSI), CH-5232 Villigen PSI (Switzerland)
Molecular characterization of organic aerosol using nanospray desorption/ electrospray ionization mass spectrometry: CalNex 2010 field study
Laboratory, Pacific Northwest National Laboratory, Richland, WA 99352, USA c Chemical and Materials Sciences molecular species were detected in the mass range of 50e400 m/z using positive mode ESI of aerosol samples in the 0.18e0.32 mm size range. Our analysis focused on identification of two main groups: compounds
Goldstein, Allen
Standard test method for isotopic analysis of hydrolyzed uranium hexafluoride and uranyl nitrate solutions by thermal ionization mass spectrometry
1.1 This method applies to the determination of isotopic composition in hydrolyzed nuclear grade uranium hexafluoride. It covers isotopic abundance of 235U between 0.1 and 5.0 % mass fraction, abundance of 234U between 0.0055 and 0.05 % mass fraction, and abundance of 236U between 0.0003 and 0.5 % mass fraction. This test method may be applicable to other isotopic abundance providing that corresponding standards are available. 1.2 This test method can apply to uranyl nitrate solutions. This can be achieved either by transforming the uranyl nitrate solution to a uranyl fluoride solution prior to the deposition on the filaments or directly by depositing the uranyl nitrate solution on the filaments. In the latter case, a calibration with uranyl nitrate standards must be performed. 1.3 This test method can also apply to other nuclear grade matrices (for example, uranium oxides) by providing a chemical transformation to uranyl fluoride or uranyl nitrate solution. 1.4 This standard does not purport to address al...
American Society for Testing and Materials. Philadelphia
Matrixassisted laser desorption/ionization mass spectrometric analysis of aliphatic biodegradable photoluminescent polymers
established that the new ILMs provided good spottospot reproducibility and high ionization efficiency compared/ionization mass spectrometry (MALDIMS). The polymers, formed by a condensation reaction of three components
Yang, Jian
Linear electric field mass spectrometry
A mass spectrometer and methods for mass spectrometry are described. The apparatus is compact and of low weight and has a low power requirement, making it suitable for use on a space satellite and as a portable detector for the presence of substances. High mass resolution measurements are made by timing ions moving through a gridless cylindrically symmetric linear electric field. 8 figs.
McComas, D.J.; Nordholt, J.E.
Symposium on accelerator mass spectrometry
The area of accelerator mass spectrometry has expanded considerably over the past few years and established itself as an independent and interdisciplinary research field. Three years have passed since the first meeting was held at Rochester. A Symposium on Accelerator Mass Spectrometry was held at Argonne on May 11-13, 1981. In attendance were 96 scientists of whom 26 were from outside the United States. The present proceedings document the program and excitement of the field. Papers are arranged according to the original program. A few papers not presented at the meeting have been added to complete the information on the status of accelerator mass spectrometry. Individual papers were prepared separately for the data base.
Airfoil sampling of a pulsed Laval beam with tunable vacuum ultraviolet (VUV) synchrotron ionization quadrupole mass spectrometry: Application to low--temperature kinetics and product detection
A new pulsed Laval nozzle apparatus with vacuum ultraviolet (VUV) synchrotron photoionization quadrupole mass spectrometry is constructed to study low-temperature radicalneutralchemical reactions of importance for modeling the atmosphere of Titan and the outer planets. A design for the sampling geometry of a pulsed Laval nozzle expansion has beendeveloped that operates successfully for the determination of rate coefficients by time-resolved mass spectrometry. The new concept employs airfoil sampling of the collimated expansion withexcellent sampling throughput. Time-resolved profiles of the high Mach number gas flow obtained by photoionization signals show that perturbation of the collimated expansion by theairfoil is negligible. The reaction of C2H with C2H2 is studied at 70 K as a proof-of-principle result for both low-temperature rate coefficient measurements and product identification basedon the photoionization spectrum of the reaction product versus VUV photon energy. This approach can be used to provide new insights into reaction mechanisms occurring at kinetic ratesclose to the collision-determined limit.
Soorkia, Satchin; Liu, Chen-Lin; Savee, John D.; Ferrell, Sarah J.; Leone, Stephen R.; Wilson, Kevin R.
Mass Spectrometry | EMSL
AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE:1 First Use of Energy for All Purposes (Fuel and Nonfuel),Feet) Year Jan Feb Mar Apr May Jun Jul(Summary)morphinanInformation Desert Southwest Region serviceMissionreal-time informationScience &MapsMarketsMass
Liquid Microjunction Surface Sampling Coupled with High-Pressure Liquid Chromatography-Electrospray Ionization-Mass Spectrometry for Analysis of Drugs and Metabolites in Whole-Body Thin Tissue Sections
In this work, a commercially available autosampler was adapted to perform direct liquid microjunction (LMJ) surface sampling followed by a high-pressure liquid chromatography (HPLC) separation of the extract components and detection with electrospray ionization mass spectrometry (ESI-MS). To illustrate the utility of coupling a separation with this direct liquid extraction based surface sampling approach, four different organs (brain, lung, kidney, and liver) from whole-body thin tissue sections of propranolol dosed and control mice were examined. The parent drug was observed in the chromatograms of the surface sampling extracts from all the organs of the dosed mouse examined. In addition, two isomeric phase II metabolites of propranolol (an aliphatic and an aromatic hydroxypropranolol glucuronide) were observed in the chromatograms of the extracts from lung, kidney, and liver. Confirming the presence of one or the other or both of these glucuronides in the extract from the various organs was not possible without the separation. These drug and metabolite data obtained using the LMJ surface sampling/HPLC-MS method and the results achieved by analyzing similar samples by conventional extraction of the tissues and subsequent HPLC-MS analysis were consistent.
Fluorohydrogenate Cluster Ions in the Gas Phase: Electrospray Ionization Mass Spectrometry of the [1-Ethyl-3-methylimidazolium+][F(HF)2.3�] Ionic Liquid
Electrospray ionization of the fluorohydrogenate ionic liquid [1-ethyl-3-methylimidazolium][F(HF)2.3] ionic liquid was conducted to understand the nature of the anionic species as they exist in the gas phase. Abundant fluorohydrogenate clusters were produced; however, the dominant anion in the clusters was [FHF-], and not the fluoride-bound HF dimers or trimers that are seen in solution. Density functional theory (DFT) calculations suggest that HF molecules are bound to the clusters by about 30 kcal/mol. The DFT-calculated structures of the [FHF-]-bearing clusters show that the favored interactions of the anions are with the methynic and acetylenic hydrogen atoms on the imidazolium cation, forming planar structures similar to those observed in the solid state. A second series of abundant negative ions was also formed that contained [SiF5-] together with the imidazolium cation and the fluorohydrogenate anions that originate from reaction of the spray solution with silicate surfaces.
Gary S. Groenewold; James E. Delmore; Michael T. Benson; Tetsuya Tsuda; Rika Hagiwara
accurate mass spectrometry: Topics by E-print Network
Positive Negative *) Atomic composition Graham, Nick 2 FOCUS: TOP-DOWN MASS SPECTROMETRY Collective Mass Spectrometry Approaches Biology and Medicine Websites Summary:...
Atmospheric Solids Analysis Probe Mass Spectrometry: A New Approach...
Atmospheric Solids Analysis Probe Mass Spectrometry: A New Approach for Airborne Particle Analysis. Atmospheric Solids Analysis Probe Mass Spectrometry: A New Approach for Airborne...
New Mass Spectrometry Techniques for Studying Physical Chemistry...
Mass Spectrometry Techniques for Studying Physical Chemistry of Atmospheric Heterogeneous Processes. New Mass Spectrometry Techniques for Studying Physical Chemistry of Atmospheric...
High efficiency resonance ionization mass spectrometric analysis by external laser cavity enhancement techniques
The demand to measure high dynamic range isotope ratios on small samples with resonance ionization mass spectrometry (RIMS) continues to increase. This paper discusses high ionization efficiency methods which can be applied to continuous wave (cw) RIMS to potentially achieve several tens of percent ionization efficiencies for certain elements. The primary technique under development to achieve this is an external laser cavity which can generate very high circulating laser powers. 12 refs., 3 figs.
Johnson, S.G.; Rios, E.L.; Miller, C.M.; Fearey, B.L.
Methods for recalibration of mass spectrometry data
Disclosed are methods for recalibrating mass spectrometry data that provide improvement in both mass accuracy and precision by adjusting for experimental variance in parameters that have a substantial impact on mass measurement accuracy. Optimal coefficients are determined using correlated pairs of mass values compiled by matching sets of measured and putative mass values that minimize overall effective mass error and mass error spread. Coefficients are subsequently used to correct mass values for peaks detected in the measured dataset, providing recalibration thereof. Sub-ppm mass measurement accuracy has been demonstrated on a complex fungal proteome after recalibration, providing improved confidence for peptide identifications.
Tolmachev, Aleksey V. (Richland, WA); Smith, Richard D. (Richland, WA)
Ultrasensitive Nanoelectrospray Ionization-Mass Spectrometry using
AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE:1 First Use of Energy for All Purposes (Fuel and Nonfuel),Feet) Year Jan Feb Mar Apr MayAtmosphericNuclear SecurityTensile Strain Switched Ferromagnetism in Layeredof2014 EIAUltrafast Transformations
Electrospray ionization mass spectrometric characterization of acrylamide adducts to hemoglobin
The most common procedure to identify hemoglobin adducts has been to cleave the adducts from the protein and characterize the adducting species, by, for example, derivatization and gas chromatography/mass spectrometry. To extend these approaches we used electrospray ionization mass spectrometry (ESI-MS) to characterize adducted hemoglobin. For this we incubated [[sup 14]C]acrylamide with the purified human hemoglobin (type A[sub 0]) under conditions that yielded high adduct levels. When the hemoglobin was separated by reversed-phase high-performance liquid chromatography (HPLC), 65% of the radioactivity copurified with the [beta]-subunit. Three adducted species were prominent in the ESI mass spectrum of the intact [beta]-subunit, indicating acrylamide adduction (i.e., mass increase of 71 Da) and two addition unidentified moieties with mass increments of 102 and 135 Da. Endoproteinase Glu-C digestion of the adducted [beta]-subunit resulted in a peptide mixture that, upon reversed-phase HPLC separation, provided several radiolabeled peptides. Using ESI-MS we identified these as the V[sub 91-101] and V[sub 102-122] peptides that represent the cysteine-containing peptides of the [beta]-subunit. These results provide definitive information on acrylamide-modified human hemoglobin and demonstrate that ESI-MS provides valuable structure information on chemically adducted proteins. 30 refs., 9 figs., 3 tabs.
Springer, D.L.; Goheen, S.C.; Edmonds, C.G. (Pacific Northwest Lab., Richland, WA (United States)); Bull, R.J.; Sylvester, D.M. (Washington State Univ., Pullman, WA (United States))
High performance �?�Cf plasma desorption mass spectrometry
ABSTRACT . ACKNOWLEDGEMENT TABLE OF CONTENTS . tv LIST OF TABLES LIST OF FIGURES C~R I. INTRODUCTION tx xt A. A General Overview . 1. Particle-Induced Desorption 2. The Application of Cf PDMS in Analytical Chemistry 3. Time-of-Flight Mass... INTRODUCTION The method of 'Cf plasma desorption mass spectrometry (PDMS) is a mass spectrometric method pioneered in 1974 by Macfarlane and co-workers (1) at Texas A&M University. This method uses fission fragments (highly energetic atomic ions...
McIntire, Thomas Shane
Laser photoionization time-of-flight mass spectrometry of nitrated polycyclic aromatic hydrocarbons and nitrated heterocyclic compounds. Master's thesis
Partial Contents: Laser Desorption-Laser Photoionization Time-of-Flight Mass Spectrometry; Basic Principles of TOFMS; Factors Affecting Flight Time; Source of Broadening; Laser Desorption; Theory of Multiphoton Ionization: Application to Mass Spectrometry; Quantum Theory of MPI; Time-Dependent Perturbation Theory; Time-Dependent Coefficients; Probability of a Two-Photon Process; and Attributes of R2PI.
Noyes, R.A.
Prospects for large dynamic range isotope analysis using photon burst mass spectrometry
Photon Burst Mass Spectrometry is a relatively new and untried method which may complement and extend the impressive achievements of Resonance Ionization Mass Spectrometry and Accelerator Mass Spectrometry in the field of large dynamic range isotope analysis. Theoretical predictions indicate that measurements in the 10/sup /minus/11/ to 10/sup /minus/15/ range are possible in a reasonable period of time with zero background. Experimentally only the very first demonstrations of PBMS with stable isotopes have been completed. 8 refs., 1 fig., 1 tab.
Fairbank, W.M. Jr.; LaBelle, R.D.; Keller, R.A.; Miller, C.M.; Poths, J.; Fearey, B.L.
accuracy mass spectrometry: Topics by E-print Network
Milos 2 High Mass Accuracy and High Mass Resolving Power FT-ICR Secondary Ion Mass Spectrometry for Biological Tissue Imaging CERN Preprints Summary: Biological tissue imaging by...
Optimization Of A Mass Spectrometry Process
In this paper we present and discuss a system developed in order to optimize the mass spectrometry process of an ion implanter. The system uses a PC to control and display the mass spectrum. The operator interacts with the I/O board, that interfaces with the computer and the ion implanter by a LabVIEW code. Experimental results are shown and the capabilities of the system are discussed.
Lopes, Jose [Instituto Superior de Engenharia de Lisboa, Rua Conselheiro Emidio Navarro, 1, 1959-007 Lisbon (Portugal); Instituto Superior Tecnico, Av. Rovisco Pais, 1, 1049-001 Lisbon (Portugal); Instituto Tecnologico e Nuclear, E.N. 10, Sacavem 2686-953 (Portugal); Centro de Fisica Nuclear da Universidade de Lisboa, Av. Prof. Gama Pinto 2, 1649-003 Lisboa (Portugal); Alegria, F. Correa [Instituto Superior Tecnico, Av. Rovisco Pais, 1, 1049-001 Lisbon (Portugal); Instituto de Telecomunicacoes, Av. Rovisco Pais, 1, 1049-001 Lisbon (Portugal); Redondo, Luis [Instituto Superior de Engenharia de Lisboa, Rua Conselheiro Emidio Navarro, 1, 1959-007 Lisbon (Portugal); Centro de Fisica Nuclear da Universidade de Lisboa, Av. Prof. Gama Pinto 2, 1649-003 Lisboa (Portugal); Barradas, N. P.; Alves, E. [Instituto Tecnologico e Nuclear, E.N. 10, Sacavem 2686-953 (Portugal); Centro de Fisica Nuclear da Universidade de Lisboa, Av. Prof. Gama Pinto 2, 1649-003 Lisboa (Portugal); Rocha, Jorge [Instituto Tecnologico e Nuclear, E.N. 10, Sacavem 2686-953 (Portugal)
applying mass spectrometry: Topics by E-print Network
*) Atomic composition Graham, Nick 4 Analytical Performance of Accelerator Mass Spectrometry and Liquid Scintillation Counting for Biotechnology Websites Summary: Analytical...
Monolithic multinozzle emitters for nanoelectrospray mass spectrometry
Novel and significantly simplified procedures for fabrication of fully integrated nanoelectrospray emitters have been described. For nanofabricated monolithic multinozzle emitters (NM.sup.2 emitters), a bottom up approach using silicon nanowires on a silicon sliver is used. For microfabricated monolithic multinozzle emitters (M.sup.3 emitters), a top down approach using MEMS techniques on silicon wafers is used. The emitters have performance comparable to that of commercially-available silica capillary emitters for nanoelectrospray mass spectrometry.
Wang, Daojing (Daly City, CA); Yang, Peidong (Kensington, CA); Kim, Woong (Seoul, KR); Fan, Rong (Pasadena, CA)
Tandem Mass Spectrometry for the Direct Assay of Lysosomal Enzymes in
. Mucopolysaccharidosis type I (MPS-I)4 is a lysosomal storage disorder caused by the deficiency of -L- iduronidase (Id-Scheie syndromes. IdA is essential for the degradation within lysosomes of the glycosamino- glycans dermatan recognition of MPS-I. Flu- orometric, radiometric, and electrospray ionization tandem mass spectrometry (ESI
Gelb, Michael
Characterization of Individual Nanoparticles and Applications of Nanoparticles in Mass Spectrometry
information from single massive cluster impacts. The clusters used in this secondary ion mass spectrometry (SIMS) technique are Au4004+ and C60+. The ionized ejecta from each impact are recorded individually which allows to identify ions emitted from a surface...
Rajagopal Achary, Sidhartha Raja
B American Society for Mass Spectrometry, 2011 DOI: 10.1007/s13361-011-0115-y
@snu.ac.kr #12;ionization, (B) low-energy multiple CA in the plume, and (C) post-source high-energy CAB American Society for Mass Spectrometry, 2011 DOI: 10.1007/s13361-011-0115-y J. Am. Soc. Mass-Recognized in MALDI Mass Spectrometry Yong Jin Bae,1 Jeong Hee Moon,2 Myung Soo Kim1 1 Department of Chemistry, Seoul
Kim, Myung Soo
Analysis of MALDI FT-ICR Mass Spectrometry Data: a Time Series Donald A. Barkauskasa, Scott R. Kronewitterb, Carlito B. Lebrillab, and David M. Rockec
Analysis of MALDI FT-ICR Mass Spectrometry Data: a Time Series Approach Donald A. Barkauskasa/ionization Fourier transform ion cyclotron resonance mass spectrometry is a technique for high mass gamma distribution with varying scale parameter but constant shape parameter and exponent. This enables
Rocke, David M.
Nanoelectrospray ion generation for high-throughput mass spectrometry using a micromachined ultrasonic ejector array
Ultrasonic electrospray ionization (ESI) for high-throughput mass spectrometry is demonstrated using a silicon micromachined microarray. The device uses a micromachined ultrasonic atomizer operating in the 900 kHz-2.5 MHz range for droplet generation and a metal electrode in the fluid cavity for ionization. Since the atomization and ionization processes are separated, the ultrasonic ESI source shows the potential for operation at low voltages with a wide range of solvents in contrast with conventional capillary ESI technology. This is demonstrated using the ultrasonic ESI microarray to obtain the mass spectrum of a 10 {mu}M reserpine sample on a time of flight mass spectrometer with 197:1 signal-to-noise ratio at an ionization potential of 200 V.
Aderogba, S.; Meacham, J.M.; Degertekin, F.L.; Fedorov, A.G.; Fernandez, F.M. [G.W. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States); School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States)
Improving liquid chromatography-mass spectrometry sensitivity...
sensitivity using a subambient pressure ionization with nanoelectrospray (SPIN Abstract: In this work the Subambient Pressure Ionization with Nanoelectrospray (SPIN) ion...
analytical mass spectrometry: Topics by E-print Network
analytical methods for solving a variety of molecular structure problems. Among high. Extension of mass spectrometry to the analysis of high molecular weight materials,...
Multinozzle Emitter Arrays for Nanoelectrospray Mass Spectrometry
Mass spectrometry (MS) is the enabling technology for proteomics and metabolomics. However, dramatic improvements in both sensitivity and throughput are still required to achieve routine MS-based single cell proteomics and metabolomics. Here, we report the silicon-based monolithic multinozzle emitter array (MEA), and demonstrate its proof-of-principle applications in high-sensitivity and high-throughput nanoelectrospray mass spectrometry. Our MEA consists of 96 identical 10-nozzle emitters in a circular array on a 3-inch silicon chip. The geometry and configuration of the emitters, the dimension and number of the nozzles, and the micropillar arrays embedded in the main channel, can be systematically and precisely controlled during the microfabrication process. Combining electrostatic simulation and experimental testing, we demonstrated that sharpened-end geometry at the stem of the individual multinozzle emitter significantly enhanced the electric fields at its protruding nozzle tips, enabling sequential nanoelectrospray for the high-density emitter array. We showed that electrospray current of the multinozzle emitter at a given total flow rate was approximately proportional to the square root of the number of its spraying-nozzles, suggesting the capability of high MS sensitivity for multinozzle emitters. Using a conventional Z-spray mass spectrometer, we demonstrated reproducible MS detection of peptides and proteins for serial MEA emitters, achieving sensitivity and stability comparable to the commercial capillary emitters. Our robust silicon-based MEA chip opens up the possibility of a fully-integrated microfluidic system for ultrahigh-sensitivity and ultrahigh-throughput proteomics and metabolomics.
Mao, Pan; Wang, Hung-Ta; Yang, Peidong; Wang, Daojing
Top-Down Mass Spectrometry Imaging of Intact Proteins by LAESI FT-ICR MS
Laser Ablation Electrospray Ionization is a recent development in mass spectrometry imaging. It has been shown that lipids and small metabolites can be imaged in various samples such as plant material, tissue sections or bacterial colonies without anysample pre-treatment. Further, laser ablation electrospray ionization has been shown to produce multiply charged protein ions from liquids or solid surfaces. This presents a means to address one of the biggest challenges in mass spectrometry imaging; the identification of proteins directly from biological tissue surfaces. Such identification is hindered by the lack of multiply charged proteins in common MALDI ion sources and the difficulty of performing tandem MS on such large, singly charged ions. We present here top-down identification of intact proteins from tissue with a LAESI ion source combined with a hybrid ion-trap FT-ICR mass spectrometer. The performance of the system was first tested with a standard protein with ECD and IRMPD fragmentation to prove the...
Kiss, Andr�s; Reschke, Brent R; Powell, Matthew J; Heeren, Ron M A
RAPID COMMUNICATIONS IN MASS SPECTROMETRY Rapid Commun. Mass Spectrom. 2004; 18: 27062712
mass spectrometry.7,8 The internal energy that ions acquire in the MALDI process or via colli- sional of high quality. Tandem mass spectrometry utilizing photodissociation (PD) with ultraviolet (UV) radiation be a viable alternative to CAD for tandem mass spectrometry of large molecules because the energy requirement
Laser desorption mass spectrometry for fast DNA analysis
During the past few years, major effort has been directed toward developing mass spectrometry to measure biopolymers because of the great potential benefit to biomedical research. Hellenkamp and his co-workers were the first to report that large polypeptide molecules can be ionized and detected without significant fragmentation when a greater number of nicotinic acid molecules are used as a matrix. This method is now well known as matrix-assisted laser desorption/ionization (MALDI). Since then, various groups have reported measurements of very large proteins by MALDI. Reliable protein analysis by MALDI is more or less well established. However, the application of MALDI to nucleic acids analysis has been found to be much more difficult. Most research on the measurement of nucleic acid by MALDI were stimulated by the Human Genome Project. Up to now, the only method for reliable routine analysis of nucleic acid is gel electrophoresis. Different sizes of nucleic acids can be separated in gel medium when a high electric field is applied to the gel. However, the time needed to separate different sizes of DNA segments usually takes from several minutes to several hours. If MALDI can be successfully used for nucleic acids analysis, the analysis time can be reduced to less than I millisecond. In addition, no tagging with radioactive materials or chemical dyes is needed. In this work, we will review recent progress related to MALDI for DNA analysis.
Chen, C.H.; Ch`ang, L.Y.; Taranenko, N.I.; Allman, S.L.; Tang, K.; Matteson, K.J.
Matrix Effects in Biological Mass Spectrometry Imaging: Identification and Compensation
Matrix effects in mass spectrometry imaging (MSI) may affect the observed molecular distribution in chemical and biological systems. In this study, we introduce an experimental approach that efficiently compensates for matrix effects in nanospray desorption electrospray ionization (nano-DESI) MSI without introducing any complexity into the experimental protocol. We demonstrate compensation for matrix effects in nano-DESI MSI of phosphatidylcholine (PC) in normal and ischemic mouse brain tissue by doping the nano-DESI solvent with PC standards. Specifically, we use mouse brain tissue of a middle cerebral artery occlusion (MCAO) stroke model with an ischemic region localized to one hemisphere of the brain. Due to similar suppression in ionization of endogenous PC molecules extracted from the tissue and PC standards added to the solvent, matrix effects are eliminated by normalizing the intensity of the sodium and potassium adducts of endogenous PC to the intensity of the corresponding adduct of the PC standard. This approach efficiently compensates for signal variations resulting from differences in the local concentrations of sodium and potassium in tissue sections and from the complexity of the extracted analyte mixture derived from local variations in molecular composition.
Lanekoff, Ingela T.; Stevens, Susan; Stenzel-Poore, Mary; Laskin, Julia
Digital microfluidic sample preparation for biological mass spectrometry�
The use of mass spectrometry in the biosciences has undergone huge growth in re- cent years due to sustained effort in the development of new ionisation techniques, more powerful mass analysers and better bioinformatic ...
Stokes, Adam A.
Secondary ion mass spectrometry (SIMS)! Seminar 4 (UN)!
for compositional analysis of solid surfaces and thin films. When a surface is bombarded by high energy beam! ! Secondary ion mass spectrometry (SIMS)! Seminar 4 (UN)! ! ! ! ! ! ! ! ! Author: Nina Kovacic! ___________________________________________________________________________! ABSTRACT! ! Secondary ion mass spectrometry (SIMS) is an analytical experimental technique, used
�?umer, Slobodan
Single Cell Analysis Using Microfluidics Coupled to Ultrasensitive Mass Spectrometry
Single Cell Analysis Using Microfluidics Coupled to Ultrasensitive Mass Spectrometry PI Ryan Kelly is to combine microfluidic sample preparation and separations with the ultrasensitive mass spectrometry (MS without the need for chemical labeling. We will combine our expertise in the fields of microfluidics
On-line electrochemistry/electrospray mass spectrometry: Studies of oxidation of polycyclic aromatic hydrocarbons (PAHs)
Studies of on-line coupling of electrochemistry with mass spectrometry, i.e., {open_quotes}electrochemical mass spectrometry{close_quotes} (EC/MS) date back to work by Bruckenstein et al. in the 1970`s. In these and other early experiments, porous working electrodes or permeable membranes were usually used as the interface between the cell and the MS ionization source which exclusively employed electron ionization (EI). As a result, only volatile products of electrochemical reactions could be detected by the mass line electrochemistry/mass spectroscopy was the coupling of an mass spectrometer (EC/TS/MS) reported by Hambitzer and g an aqueous ammonium acetate thermospray buffer solution, all detected or ammoniated species in the positive ion mode or as deprotonated or acetate adduct species in the negative ion mode. Radical cations or anions were not detected. Although {open_quotes}electrochemically assisted electrospray mass spectrometry{close_quotes} has been progressing for a few years, chiefly due to the pioneering efforts of Van Berkel and coworkers, on-line coupling electrochemistry with electrospray mass spectrometry (EC/ESMS) is still a developing area because of the experimental difficulties involved, such as high voltage hazard to the electrochemistry hardware (e.g. potentiostat), and MS signal suppression caused by the presence of high concentrations of supporting electrolytes. We report the coupling of an electrochemical device on-line with electrospray mass spectrometry (EC/ESMS) to extend the potential of ESMS to detect non-polar neutral compounds, and to monitor and identify intermediates and products generated by electrochemical reactions.
Xu, Xiaoming; Lu, Wenzhe; Cole, R.B. [Univ. of New Orleans, LA (United States)] [and others
Analytical Performance of Accelerator Mass Spectrometry and Liquid Scintillation Counting for
Analytical Performance of Accelerator Mass Spectrometry and Liquid Scintillation Counting for Accelerator Mass Spectrometry, Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, California of California, San Francisco, California 94143 Accelerator mass spectrometry (AMS) has been applied
Hammock, Bruce D.
Transition of Iodine Analysis to Accelerator Mass Spectrometry
This NA 22 funded research project investigated the transition of iodine isotopic analyses from thermal ionization mass spectrometry (TIMS) to an accelerator mass spectrometry (AMS) system. Previous work (Fiscal Year 2010) had demonstrated comparable data from TIMS and AMS. With AMS providing comparable data with improved background levels and vastly superior sample throughput, improvement in the sample extraction from environmental sample matrices was needed to bring sample preparation throughput closer to the operation level of the instrument. Previous research used an extraction chemistry that was not optimized for yield or refined for reduced labor to prove the principle. This research was done to find an extraction with better yield using less labor per sample to produce a sample ready for the AMS instrument. An extraction method using tetramethyl ammonium hydroxide (TMAH) was developed for removal of iodine species from high volume air filters. The TMAH with gentle heating was superior to the following three extraction methods: ammonium hydroxide aided by sonication, acidic and basic extraction aided by microwave, and ethanol mixed with sodium hydroxide. Taking the iodine from the extraction solvent to being ready for AMS analysis was accomplished by a direct precipitation, as well as, using silver wool to harvest the iodine from the TMAH. Portions of the same filters processed in FY 2010 were processed again with the improved extraction scheme followed by successful analysis by AMS at the Swiss Federal Institute of Technology. The data favorably matched the data obtained in 2010. The time required for analysis has been reduced over the aqueous extraction/AMS approach developed in FY 2010. For a hypothetical batch of 30 samples, the AMS methodology is about 10 times faster than the traditional gas phase chemistry and TIMS analysis. As an additional benefit, background levels for the AMS method are about 1000 times lower than TIMS. This results from the fundamental mechanisms of ionization in the AMS system and which produces a beneficial cleanup of molecular interferences. Continued clean operation of the extraction process was demonstrated through blank analysis included with all sample sets analyzed. INL work showed improvement on the first year�s demonstration of AMS vs. TIMS. An improved extraction of high volume air filters followed by isotopic analysis by AMS, can be used successfully to make iodine measurements with results comparable to those obtained by filter combustion and TIMS analysis. More progress on the conversion from an extract solution to an AMS sample ready for analysis is still needed. Although the preparation scheme through AMS is already at a higher performing thoughput than TIMS, the chemical preparation cannot match the instrument capability for number of samples per day without further development.
M. L. Adamic; J. E. Olson; D. D. Jenson; J. G. Eisenmenger; M. G. Watrous
Small system for tritium accelerator mass spectrometry
Apparatus for ionizing and accelerating a sample containing isotopes of hydrogen and detecting the ratios of hydrogen isotopes contained in the sample is disclosed. An ion source generates a substantially linear ion beam including ions of tritium from the sample. A radio-frequency quadrupole accelerator is directly coupled to and axially aligned with the source at an angle of substantially zero degrees. The accelerator accelerates species of the sample having different mass to different energy levels along the same axis as the ion beam. A spectrometer is used to detect the concentration of tritium ions in the sample. In one form of the invention, an energy loss spectrometer is used which includes a foil to block the passage of hydrogen, deuterium and .sup.3 He ions, and a surface barrier or scintillation detector to detect the concentration of tritium ions. In another form of the invention, a combined momentum/energy loss spectrometer is used which includes a magnet to separate the ion beams, with Faraday cups to measure the hydrogen and deuterium and a surface barrier or scintillation detector for the tritium ions.
Roberts, Mark L. (Livermore, CA); Davis, Jay C. (Livermore, CA)
Apparatus for ionizing and accelerating a sample containing isotopes of hydrogen and detecting the ratios of hydrogen isotopes contained in the sample is disclosed. An ion source generates a substantially linear ion beam including ions of tritium from the sample. A radio-frequency quadrupole accelerator is directly coupled to and axially aligned with the source at an angle of substantially zero degrees. The accelerator accelerates species of the sample having different mass to different energy levels along the same axis as the ion beam. A spectrometer is used to detect the concentration of tritium ions in the sample. In one form of the invention, an energy loss spectrometer is used which includes a foil to block the passage of hydrogen, deuterium and [sup 3]He ions, and a surface barrier or scintillation detector to detect the concentration of tritium ions. In another form of the invention, a combined momentum/energy loss spectrometer is used which includes a magnet to separate the ion beams, with Faraday cups to measure the hydrogen and deuterium and a surface barrier or scintillation detector for the tritium ions.
Roberts, M.L.; Davis, J.C.
Mass Spectrometry-based Methods for Phosphorylation Site Mapping of
Mass Spectrometry-based Methods for Phosphorylation Site Mapping of Hyperphosphorylated Proteins spectrometry-based approach. No one approach was able to identify all phosphopeptides in the tryptic digests and detected by scintillation counting or autoradiography. The HPLC fraction or excised TLC spot is subjected
Shou, Wenying
Toward Plasma Proteome Profiling with Ion Mobility-Mass Spectrometry
Toward Plasma Proteome Profiling with Ion Mobility-Mass Spectrometry Stephen J. Valentine, Manolo D) analysis of a plasma digest sample where abundant proteins have not been removed. Protein database searches- for comparative plasma profiling studies. Keywords: ion mobility spectrometry · proteome profiling
Clemmer, David E.
E-Print Network 3.0 - alpha spectrometry 232u Sample Search Results
for thermal ionization mass spectrometry (TIMS) and 800 mg for alpha spectrom- etry. Uranium-thorium TIMS... . Alpha spectrometry was performed at the University of Iowa....
Accelerator mass spectrometry: from nuclear physics to dating
The discussion reviews the use of accelerators originally intended for nuclear physics to do high resolution mass spectrometry for the purpose of isotope dating and age estimation of materials. (GHT)
Kutschera, W.
Molecular Beam Mass Spectrometry (MBMS) (Revised) (Fact Sheet)
This fact sheet provides information about Molecular Beam Mass Spectrometry (MBMS) capabilities and applications at NREL's National Bioenergy Center. NREL has six MBMS systems that researchers and industry partners can use to understand thermochemical biomass conversion and biomass composition recalcitrance.
Not Available
accelerator mass spectrometry: Topics by E-print Network
Bousfield, George R. 2004-05-01 25 High performance ?Cf plasma desorption mass spectrometry Texas A&M University - TxSpace Summary: Track and the Dissemination of Energy. . ....
Tools for investigating cellular signaling networks by mass spectrometry
Mass spectrometry has become the tool of choice for proteomics. Its unrivaled coverage and reproducibility has positioned it head and shoulders above competing techniques for analyzing protein expression post-translational ...
Curran, Timothy Gordon
RAPID COMMUNICATIONS IN MASS SPECTROMETRY Rapid Commun. Mass Spectrom. 2005; 19: 32483252
to be that photofragment ions generated at this wavelength are similar to those from low- and high-energy CAD, and are thusRAPID COMMUNICATIONS IN MASS SPECTROMETRY Rapid Commun. Mass Spectrom. 2005; 19: 3248 of singly protonated peptides at 193 nm investigated with tandem time-of-flight mass spectrometry Jeong Hee
RAPID COMMUNICATIONS IN MASS SPECTROMETRY Rapid Commun. Mass Spectrom. 2005; 19: 24812487
chromophore dissociated efficiently when a suf- ficiently high laser pulse energy was used. Also, the pulseRAPID COMMUNICATIONS IN MASS SPECTROMETRY Rapid Commun. Mass Spectrom. 2005; 19: 2481 time-of- flight (TOF) mass spectrometry of ions generated by matrix-assisted laser desorption
Brominated Tyrosine and Polyelectrolyte Multilayer Analysis by Laser Desorption VUV Postionization and Secondary Ion Mass Spectrometry
The small molecular analyte 3,5-dibromotyrosine (Br2Y) and chitosan-alginate polyelectrolyte multilayers (PEM) with and without adsorbed Br2Y were analyzed by laser desorption postionization mass spectrometry (LDPI-MS). LDPI-MS using 7.87 eV laser and tunable 8 ? 12.5 eV synchrotron vacuum ultraviolet (VUV) radiation found that desorption of clusters from Br2Y films allowed detection by?8 eV single photon ionization. Thermal desorption and electronic structure calculations determined the ionization energy of Br2Y to be ~;;8.3?0.1 eV and further indicated that the lower ionization energies of clusters permitted their detection at?8 eV photon energies. However, single photon ionization could only detect Br2Y adsorbed within PEMs when using either higher photon energies or matrix addition to the sample. All samples were also analyzed by 25 keV Bi3 + secondary ion mass spectrometry (SIMS), with the negative ion spectra showing strong parent ion signal which complemented that observed by LDPI-MS. The negative ion SIMS depended strongly on the high electron affinity of this specific analyte and the analyte?s condensed phase environment.
University of Illinois at Chicago; Blaze, Melvin M. T.; Takahashi, Lynelle; Zhou, Jia; Ahmed, Musahid; Gasper, Gerald; Pleticha, F. Douglas; Hanley, Luke
Department of Chemistry Mass Spectrometry Sample Submission Form
's ID. · You are responsible to pick up your samples within 7 days after the analysis. · Please call 801: [ ] Standard (LRMS) [ ] Exact Mass (HRMS) Ionization type: [ ] ESI [ ] MALDI [ ] EI (GC/MS only) Scans required
Simons, Jack
Secondary Ion Mass Spectrometry Imaging of Dictyostelium discoideum Aggregation Streams
High resolution imaging mass spectrometry could become a valuable tool for cell and developmental biology, but both, high spatial and mass spectral resolution are needed to enable this. In this report, we employed Bi3 bombardment time-of-flight (Bi3 ToF-SIMS) and C60 bombardment Fourier transform ion cyclotron resonance secondary ion mass spectrometry (C60 FTICR-SIMS) to image Dictyostelium discoideum aggregation streams. Nearly 300 lipid species were identified from the aggregation streams. High resolution mass spectrometry imaging (FTICR-SIMS) enabled the generation of multiple molecular ion maps at the nominal mass level and provided good coverage for fatty acyls, prenol lipids, and sterol lipids. The comparison of Bi3 ToF-SIMS and C60 FTICR-SIMS suggested that while the first provides fast, high spatial resolution molecular ion images, the chemical complexity of biological samples warrants the use of high resolution analyzers for accurate ion identification.
Debord, J. Daniel; Smith, Donald F.; Anderton, Christopher R.; Heeren, Ronald M.; Pasa-Tolic, Ljiljana; Gomer, Richard H.; Fernandez-Lima, Francisco A.
Facilitation of protein 3-D structure determination using enhanced peptide amide deuterium exchange mass spectrometry (DXMS)
and Energy Change at High Resolution Employing Enhanced Peptide Amide Deuterium Exchange- Mass Spectrometry (
Pantazatos, Dennis Peter
Determination of the stellar (n,$\\gamma$) cross section of $^{54}Fe$ with accelerator mass spectrometry
Determination of the stellar (n,$\\gamma$) cross section of $^{54}Fe$ with accelerator mass spectrometry
Coquard, L; Dillmann, I; Wallner, A; Knie, K; Kutschera, W
Apparatus for preparing a sample for mass spectrometry
An apparatus is described for preparing a sample for analysis by a mass spectrometer system. The apparatus has an entry chamber and an ionization chamber separated by a skimmer. A capacitor having two space-apart electrodes followed by one or more ion-imaging lenses is disposed in the ionization chamber. The chamber is evacuated and the capacitor is charged. A valve injects a sample gas in the form of sample pulses into the entry chamber. The pulse is collimated by the skimmer and enters the ionization chamber. When the sample pulse passes through the gap between the electrodes, it discharges the capacitor and is thereby ionized. The ions are focused by the imaging lenses and enter the mass analyzer, where their mass and charge are analyzed. 1 figures.
Villa-Aleman, E.
Synchrotron based mass spectrometry to investigate the molecular properties of mineral-organic associations
Soil organic matter (OM) is important because its decay drives life processes in the biosphere. Analysis of organic compounds in geological systems is difficult because of their intimate association with mineral surfaces. To date there is no procedure capable of quantitatively separating organic from mineral phases without creating artifacts or mass loss. Therefore, analytical techniques that can (a) generate information about both organic and mineral phases simultaneously and (b) allow the examination of predetermined high-interest regions of the sample as opposed to conventional bulk analytical techniques are valuable. Laser Desorption Synchrotron Postionization (synchrotron-LDPI) mass spectrometry is introduced as a novel analytical tool to characterize the molecular properties of organic compounds in mineral-organic samples from terrestrial systems, and it is demonstrated that when combined with Secondary Ion Mass Spectrometry (SIMS), can provide complementary information on mineral composition. Mass spectrometry along a decomposition gradient in density fractions, verifies the consistency of our results with bulk analytical techniques. We further demonstrate that by changing laser and photoionization energies, variations in molecular stability of organic compounds associated with mineral surfaces can be determined. The combination of synchrotron-LDPI and SIMS shows that the energetic conditions involved in desorption and ionization of organic matter may be a greater determinant of mass spectral signatures than the inherent molecular structure of the organic compounds investigated. The latter has implications for molecular models of natural organic matter that are based on mass spectrometric information.
Liu, Suet Yi; Kleber, Markus; Takahashi, Lynelle K.; Nico, Peter; Keiluweit, Marco; Ahmed, Musahid
Coming to a hospital near you: mass spectrometry imaging
Berkeley Lab's Ben Bowen discusses "Coming to a hospital near you: mass spectrometry imaging" in this Oct. 28, 2013 talk, which is part of a Science at the Theater event entitled Eight Big Ideas. Go here to watch the entire event with all 8 speakers.
Bowen, Ben
ScienceCinema (OSTI)
Absorption Mode FT-ICR Mass Spectrometry Imaging
Fourier transform ion cyclotron resonance mass spectrometry offers the highest mass resolving power for molecular imaging experiments. This high mass resolving power ensures that closely spaced peaks at the same nominal mass are resolved for proper image generation. Typically higher magnetic fields are used to increase mass resolving power. However, a gain in mass resolving power can also be realized by phase correction of the data for absorption mode display. In addition to mass resolving power, absorption mode offers higher mass accuracy and signal-to-noise ratio over the conventional magnitude mode. Here we present the first use of absorption mode for Fourier transform ion cyclotron resonance mass spectrometry imaging. The Autophaser algorithm is used to phase correct each spectrum (pixel) in the image and then these parameters are used by the Chameleon work-flow based data processing software to generate absorption mode ?Datacubes? for image and spectral viewing. Absorption mode reveals new mass and spatial features that are not resolved in magnitude mode and results in improved selected ion image contrast.
Smith, Donald F.; Kilgour, David P.; Konijnenburg, Marco; O'Connor, Peter B.; Heeren, Ronald M.
Mass spectrometry of proteins of known mass Andrew D. Miranker*
deter- mination has two significant advantages. First, the mass accuracy under these conditions to the orifice of the mass analyzer. As a result, there is a local separation of charges at the tip
Miranker, Andrew
Tandem Mass Spectrometry identifies many mouse brain O-GlcNAcylated...
Tandem Mass Spectrometry identifies many mouse brain O-GlcNAcylated proteins including EGF domain-specific O-GlcNAc transferase Tandem Mass Spectrometry identifies many mouse brain...
Picoelectrospray Ionization Mass Spectrometry Using Narrow-bore Chemically
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High-Resolution Desorption Electrospray Ionization Mass Spectrometry...
between different mechanisms of chemical aging. Citation: Laskin J, A Laskin, PJ Roach, GW Slysz, GA Anderson, S Nizkorodov, DL Bones, and L Nguyen.2010."High-Resolution...
High-Resolution Desorption Electrospray Ionization Mass Spectrometry for
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High-Resolution Electrospray Ionization Mass Spectrometry Analysis of
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Applications of High-Resolution Electrospray Ionization Mass Spectrometry
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Miniature quadrupole mass spectrometer having a cold cathode ionization source
An improved quadrupole mass spectrometer is described. The improvement lies in the substitution of the conventional hot filament electron source with a cold cathode field emitter array which in turn allows operating a small QMS at much high internal pressures then are currently achievable. By eliminating of the hot filament such problems as thermally "cracking" delicate analyte molecules, outgassing a "hot" filament, high power requirements, filament contamination by outgas species, and spurious em fields are avoid all together. In addition, the ability of produce FEAs using well-known and well developed photolithographic techniques, permits building a QMS having multiple redundancies of the ionization source at very low additional cost.
Felter, Thomas E. (Livermore, CA)
Chip-Scale Quadrupole Mass Filters for Portable Mass Spectrometry
We report the design, fabrication, and characterization of a new class of chip-scale quadrupole mass filter (QMF). The devices are completely batch fabricated using a wafer-scale process that integrates the quadrupole ...
Cheung, Kerry
Charge Prediction of Lipid Fragments in Mass Spectrometry
An artificial neural network is developed for predicting which fragment is charged and which fragment is neutral for lipid fragment pairs produced from a liquid chromatography tandem mass spectrometry simulation process. This charge predictor is integrated into software developed at PNNL for in silico spectra generation and identification of metabolites known as Met ISIS. To test the effect of including charge prediction in Met ISIS, 46 lipids are used which show a reduction in false positive identifications when the charge predictor is utilized.
Schrom, Brian T.; Kangas, Lars J.; Ginovska, Bojana; Metz, Thomas O.; Miller, John H.
Characterization of Coordination Complexes by Desorption Electrospray Mass Spectrometry with a Capillary Target
Metal coordination complexes were formed directly from liquid surfaces using desorption electrospray ionization (DESI) mass spectrometry. The approach is attractive because it separates complexities of ESI spray droplet formation from delivery of the analyte solution, and thereby gets around difficulty resulting from alteration of the spray process by changes in solution chemistry. Cs+, Ba2+, and La3+ coordination complexes were formed using 18-crown-6 (18c6) and triethylphosphate (TEP) as ligands (L), that had the general formula [Mn+(NO3-)n-1(L)m]+. Formation of singly charged cation complexes was preferred, with charge reduction at the metal site accomplished by attachment of nitrate. Using TEP as a model phosphoryl ligand, alkali metals coordinate with up to three ligands, with Cs+ preferring fewer than Na+. Ba2+ and La3+ are formed as ion pair complexes [Ba(NO3)]+ and [La(NO3)2]+, and both will coordinate with up to four TEP ligands. Using 18c6, Cs+ forms a bis-ligand complex. In contrast, [Ba(NO3)]+ prefers a single 18c6 ligand, while La forms mainly [La(NO3)2(18c6)]+, for which DFT calculations suggested a structure in which the nitrate ligands occupy pseudo-axial positions on opposing sides of the crown. Lower abundances of bis-18c6 complexes were also formed together with doubly charged [La(NO3)(18c6)n]2+ complexes (n = 2 � 4). The results suggest an alternative strategy for probing metal speciation in solution that is less perturbed by the droplet formation and ionization mechanisms operating in conventional electrospray ionization mass spectrometry.
Gary S. Groenewold; Anthony D. Appelhans; Michael E. McIlwain; Garold L. Gresham
JOURNAL OF MASS SPECTROMETRY J. Mass Spectrom. 2003; 38: 277282
tandem mass spectrom- etry even isomerizations such as isoaspartate formation are detectable.3 Low-energy, nuclear and endosomal morphology, a defect in fluid-phase uptake and an impairment in normal cytokinesis.1.02 derived from acrylamide-modified peptides.8 These fragmentation reactions can be utilized for the spe-
Manstein, Dietmar J.
Fourier transform mass spectrometry of high-mass biomolecules
In this report the authors present an overview of the use of FTMS for the analysis of large biomolecules, with emphasis on recent developments in coupling ESI and MALDI with FTMS. A simple description of the principles of FTMS operation and experimental factors that are relevant to the examination of large molecules are also presented. The examples represent state-of-the-art capabilities of FTMS. On the basis of early reports, it is apparent that the applications of FTMS for the analysis of biopolymers will expand rapidly in the near future. Although many different types of mass analyzers are compatible with FAB, ESI, and MALDI, FTMS has exhibited particular potential for high sensitivity, accurate mass measurement, high-mass resolution, and structural characterization of large biopolymers. The recent results obtained with both ESI-FTMS and MALDI-FTMS are very exciting with respect to both fundamental advances in the capabilities of FTMS and potential applications in the biochemical laboratory. 63 refs., 6 figs., 1 tab.
Buchanan, M.V.; Hettich, R.L. (Oak Ridge National Lab., TN (United States))
Structural determination of intact proteins using mass spectrometry
The present invention relates to novel methods of determining the sequence and structure of proteins. Specifically, the present invention allows for the analysis of intact proteins within a mass spectrometer. Therefore, preparatory separations need not be performed prior to introducing a protein sample into the mass spectrometer. Also disclosed herein are new instrumental developments for enhancing the signal from the desired modified proteins, methods for producing controlled protein fragments in the mass spectrometer, eliminating complex microseparations, and protein preparatory chemical steps necessary for cross-linking based protein structure determination.Additionally, the preferred method of the present invention involves the determination of protein structures utilizing a top-down analysis of protein structures to search for covalent modifications. In the preferred method, intact proteins are ionized and fragmented within the mass spectrometer.
Kruppa, Gary (San Francisco, CA); Schoeniger, Joseph S. (Oakland, CA); Young, Malin M. (Livermore, CA)
Laser Desorption Postionization Mass Spectrometry of Antibiotic-Treated Bacterial Biofilms using Tunable Vacuum Ultraviolet Radiation
Laser desorption postionization mass spectrometry (LDPI-MS) with 8.0 ? 12.5 eV vacuum ultraviolet synchrotron radiation is used to single photon ionize antibiotics andextracellular neutrals that are laser desorbed both neat and from intact bacterial biofilms. Neat antibiotics are optimally detected using 10.5 eV LDPI-MS, but can be ionized using 8.0 eV radiation, in agreement with prior work using 7.87 eV LDPI-MS. Tunable vacuum ultraviolet radiation also postionizes laser desorbed neutrals of antibiotics and extracellular material from within intact bacterial biofilms. Different extracellular material is observed by LDPI-MS in response to rifampicin or trimethoprim antibiotic treatment. Once again, 10.5 eV LDPI-MS displays the optimum trade-off between improved sensitivity and minimum fragmentation. Higher energy photons at 12.5 eV produce significant parent ion signal, but fragment intensity and other low mass ions are also enhanced. No matrix is added to enhance desorption, which is performed at peak power densities insufficient to directly produce ions, thus allowing observation of true VUV postionization mass spectra of antibiotic treated biofilms.
Gasper, Gerald L.; Takahashi, Lynelle K.; Zhou, Jia; Ahmed, Musahid; Moore, Jerry F.; Hanley, Luke
Future Directions of Structural Mass Spectrometry using Hydroxyl Radical Footprinting
Hydroxyl radical protein footprinting coupled to mass spectrometry has been developed over the last decade and has matured to a powerful method for analyzing protein structure and dynamics. It has been successfully applied in the analysis of protein structure, protein folding, protein dynamics, and protein-protein and protein-DNA interactions. Using synchrotron radiolysis, exposure of proteins to a 'white' X-ray beam for milliseconds provides sufficient oxidative modification to surface amino acid side chains, which can be easily detected and quantified by mass spectrometry. Thus, conformational changes in proteins or protein complexes can be examined using a time-resolved approach, which would be a valuable method for the study of macromolecular dynamics. In this review, we describe a new application of hydroxyl radical protein footprinting to probe the time evolution of the calcium-dependent conformational changes of gelsolin on the millisecond timescale. The data suggest a cooperative transition as multiple sites in different molecular subdomains have similar rates of conformational change. These findings demonstrate that time-resolved protein footprinting is suitable for studies of protein dynamics that occur over periods ranging from milliseconds to seconds. In this review, we also show how the structural resolution and sensitivity of the technology can be improved as well. The hydroxyl radical varies in its reactivity to different side chains by over two orders of magnitude, thus oxidation of amino acid side chains of lower reactivity are more rarely observed in such experiments. Here we demonstrate that the selected reaction monitoring (SRM)-based method can be utilized for quantification of oxidized species, improving the signal-to-noise ratio. This expansion of the set of oxidized residues of lower reactivity will improve the overall structural resolution of the technique. This approach is also suggested as a basis for developing hypothesis-driven structural mass spectrometry experiments.
J Kiselar; M Chance
Fission Yield Measurements by Inductively Coupled Plasma Mass-Spectrometry
Correct prediction of the fission products inventory in irradiated nuclear fuels is essential for accurate estimation of fuel burnup, establishing proper requirements for spent fuel transportation and storage, materials accountability and nuclear forensics. Such prediction is impossible without accurate knowledge of neutron induced fission yields. Unfortunately, the accuracy of the fission yields reported in the ENDF/B-VII.0 library is not uniform across all of the data and much of the improvement is desired for certain isotopes and fission products. We discuss our measurements of cumulative fission yields in nuclear fuels irradiated in thermal and fast reactor spectra using Inductively Coupled Plasma Mass Spectrometry.
Irina Glagolenko; Bruce Hilton; Jeffrey Giglio; Daniel Cummings; Karl Grimm; Richard McKnight
Mass Spectrometry imaging of plant metabolites | The Ames Laboratory
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atomic mass spectrometry: Topics by E-print Network
Negative *) Atomic composition Graham, Nick 3 Prospects in Analytical Atomic Spectrometry CERN Preprints Summary: Tendencies in five main branches of atomic spectrometry...
Accelerator Mass Spectrometry | U.S. DOE Office of Science (SC...
Office of Science (SC) Website
Mass Spectrometry at ANL and ORNL Developed at: Argonne National Laboratory (ANL), Oak Ridge National Laboratory (ORNL) Developed in: Current Result of NP research: Basic NP...
Method for predicting peptide detection in mass spectrometry
A method of predicting whether a peptide present in a biological sample will be detected by analysis with a mass spectrometer. The method uses at least one mass spectrometer to perform repeated analysis of a sample containing peptides from proteins with known amino acids. The method then generates a data set of peptides identified as contained within the sample by the repeated analysis. The method then calculates the probability that a specific peptide in the data set was detected in the repeated analysis. The method then creates a plurality of vectors, where each vector has a plurality of dimensions, and each dimension represents a property of one or more of the amino acids present in each peptide and adjacent peptides in the data set. Using these vectors, the method then generates an algorithm from the plurality of vectors and the calculated probabilities that specific peptides in the data set were detected in the repeated analysis. The algorithm is thus capable of calculating the probability that a hypothetical peptide represented as a vector will be detected by a mass spectrometry based proteomic platform, given that the peptide is present in a sample introduced into a mass spectrometer.
Kangas, Lars [West Richland, WA; Smith, Richard D [Richland, WA; Petritis, Konstantinos [Richland, WA
Ion Mobility Spectrometry � Mass Spectrometry Performance Using Electrodynamic Ion Funnels and Elevated Drift Gas Pressures
The ability of ion mobility spectrometry coupled with mass spectrometry (IMS-MS) to characterize biological mixtures has been illustrated over the past eight years. However, the challenges posed by the extreme complexity of many biological samples have demonstrated the need for higher resolution IMS-MS measurements. We have developed a higher resolution ESI-IMS-TOF MS by utilizing high pressure electrodynamic ion funnels at both ends of the IMS drift cell and operating the drift cell at an elevated pressure compared to a previous design. The ESI-IMS-TOF MS instrument consists of an ESI source, an hourglass ion funnel used for ion accumulation/injection into an 88 cm drift cell followed by a 10 cm ion funnel and a commercial orthogonal time-of-flight mass spectrometer providing high mass measurement accuracy. It was found that the rear (exit) ion funnel could be effectively operated as an extension of the drift cell when the DC fields were matched, allowing the instrument to have an effective drift region of 98 cm. Two differentially pumped quadrupole regions were used to couple the IMS and TOF MS to focus and minimize the ion transient time between the stages. The resolution of the instrument was evaluated at pressures ranging from 4 to12 Torr and ion mobility drift voltages of 16 V/cm (4 Torr) to 43 V/cm (12 Torr). An increase in resolution from 55 to 80 was observed from 4 to 12 Torr nitrogen drift gas with no loss in sensitivity. Given the increased usage of ion funnels prior to ion mobility separations, additional attention was directed towards the influence of drift gas on the observed ion populations trapped and transmitted using an electrodynamic ion funnel. The choice of drift gas was shown to influence the degree of ion heating and relative trapping efficiency within the ion funnel.
Baker, Erin Shammel; Clowers, Brian H.; Li, Fumin; Tang, Keqi; Tolmachev, Aleksey V.; Prior, David C.; Belov, Mikhail E.; Smith, Richard D.
Low-level 14C measurements and Accelerator Mass Spectrometry
Accelerator Mass Spectrometry (AMS) and isotope enrichment were used in 1991 to estimate that the 14C content of methane in natural gas was {<=}1.6x10-18 of the total carbon. The low content of 14C in underground hydrocarbons was verified later in the remarkable results from the Borexino test scintillation counter for solar neutrino studies. Since then studies of the 14C background problem have demonstrated that much of the background originally observed in the AMS measurements can, in principle, be eliminated. However, many difficulties and other backgrounds are to be faced as the limit for AMS is pushed still further towards possibly a ratio of < 10-21. These will be discussed.
Litherland, A.E.; Beukens, R.P.; Zhao, X.-L.; Kieser, W.E. [IsoTrace Laboratory, University of Toronto, Toronto, ON, M5S 1A7 (Canada); Gove, H.E. [IsoTrace Laboratory, University of Toronto, Toronto, ON, M5S 1A7 (Canada); Department of Physics and Astronomy, University of Rochester, Rochester, NY, 14627-0171 (United States)
Dating Studies of Elephant Tusks Using Accelerator Mass Spectrometry
A new method for determining the year of birth, the year of death, and hence, the age at death, of post-bomb and recently deceased elephants has been developed. The technique is based on Accelerator Mass Spectrometry radiocarbon analyses of small-sized samples extracted from along the length of a ge-line of an elephant tusk. The measured radiocarbon concentrations in the samples from a tusk can be compared to the {sup 14}C atmospheric bomb-pulse curve to derive the growth years of the initial and final samples from the tusk. Initial data from the application of this method to two tusks will be presented. Potentially, the method may play a significant role in wildlife management practices of African national parks. Additionally, the method may contribute to the underpinnings of efforts to define new international trade regulations, which could, in effect, decrease poaching and the killing of very young animals.
Sideras-Haddad, E; Brown, T A
Focus on Advancing High Performance Mass Spectrometry, Honoring Dr. Richard D. Smith, Recipient of the 2013 Award for a Distinguished Contribution in Mass Spectrometry
This special focus issue of the Journal of the American Society for Mass Spectrometry celebrates the accomplishments of Dr. Richard D. Smith, the recipient of the 2013ASMS Award for a Distinguished Contribution in Mass Spectrometry, and who serves as a Battelle Fellow, Chief Scientist in the Biological Sciences Division, and Director of Proteomics Research at Pacific Northwest National Laboratory (PNNL) in Richland, WA. The award is for his development of the electrodynamic ion funnel.
Baker, Erin Shammel; Muddiman, David C.; Loo, Joseph
In situ characterization of GaN quantum dot growth with reflection high-energy electron diffraction and line-of-sight mass spectrometry
mass spectrometry and re?ection high-energy electronmass spectrometry ?QMS? and re?ection high-energy electron
Brown, J S; Koblmuller, G; Averbeck, R; Riechert, H; Speck, J S
Ga adsorbate on (0001) GaN: In situ characterization with quadrupole mass spectrometry and reflection high-energy electron diffraction
Brown, J S; Koblmuller, G; Wu, F; Averbeck, R; Riechert, H; Speck, J S
High-Speed Tandem Mass Spectrometric in Situ Imaging by Nanospray...
in Situ Imaging by Nanospray Desorption Electrospray Ionization Mass Spectrometry. High-Speed Tandem Mass Spectrometric in Situ Imaging by Nanospray Desorption Electrospray...
International Journal of Mass Spectrometry 288 (2009) 1621 Contents lists available at ScienceDirect
International Journal of Mass Spectrometry 288 (2009) 1621 Contents lists available at ScienceDirect International Journal of Mass Spectrometry journal homepage: www.elsevier.com/locate/ijms Utility of reaction-MS2 and PD-MS3 were combined, demonstrating the utility of transient ion detection by PD-MS3
International Journal of Mass Spectrometry 287 (2009) 105113 Contents lists available at ScienceDirect
to deposit more internal energy into these clusters, providing access to alternative, high energyInternational Journal of Mass Spectrometry 287 (2009) 105113 Contents lists available at ScienceDirect International Journal of Mass Spectrometry journal homepage: www.elsevier.com/locate/ijms Influence of cluster
Wysocki, Vicki H.
OpenMSI: A High-Performance Web-Based Platform for Mass Spectrometry Imaging
OpenMSI: A High-Performance Web-Based Platform for Mass Spectrometry Imaging Oliver Rübel, AnnetteMSI: A High-Performance Web-Based Platform for Mass Spectrometry Imaging Oliver Rubel,* Annette Greiner. Acknowledgements: This work was supported by and used resources of the National Energy Research Scientific
fragmentation mechanisms of protonated peptides is discussed and demonstrated. High internal energy deposition in understandingpeptide fragmentation by low-energy tandem mass spectrometry. KEYWORDS: surface-induced dissociationJOURNAL OF MASS SPECTROMETRY, VOL. 31, 339-350 (1996) SPECIAL FEATURE: PERSPECTIVE Surface
Human vitamin B12 absorption measurement by accelerator mass spectrometry using specifically
Human vitamin B12 absorption measurement by accelerator mass spectrometry using specifically for Accelerator Mass Spectrometry, Lawrence Livermore National Laboratory, Livermore, CA 94551 is the suspected cause. The test involves ingestion of a physiological quantity of B12 labeled with gamma
California at Davis, University of
Method for analyzing the mass of a sample using a cold cathode ionization source mass filter
Felter, Thomas E.
Improving the Sensitivity of Mass Spectrometry by Using a New Sheath Flow Electrospray Emitter Array at Subambient Pressures
Arrays of chemically etched emitters with individualized sheath gas capillaries have been developed to enhance electrospray ionization (ESI) at subambient pressures. By including an emitter array in a subambient pressure ionization with nanoelectrospray (SPIN) source, ionization and transmission efficiency can be maximized allowing for increased sensitivity in mass spectrometric analyses. The SPIN source eliminates the major ion losses at conventional ESI-mass spectrometry (MS) interface by placing the emitter in the first vacuum region of the instrument. To facilitate stable electrospray currents in such conditions we have developed an improved emitter array with individualized sheath gas around each emitter. The utility of the new emitter arrays for generating stable multi-electrosprays at subambient pressures was probed by coupling the emitter array/SPIN source with a time of flight (TOF) mass spectrometer. The instrument sensitivity was compared between single emitter/SPIN-MS and multi-emitter/SPIN-MS configurations using an equimolar solution of 9 peptides. An increase in sensitivity correlative to the number of emitters in the array was observed.
Cox, Jonathan T.; Marginean, Ioan; Kelly, Ryan T.; Smith, Richard D.; Tang, Keqi
Size Characterization of Colloidal Platinum Nanoparticles by MALDI-TOF Mass Spectrometry
In this work, matrix assisted laser desorption ionization-time-of-flight (MALDI-TOF) mass spectrometry (MS) has been utilized to characterize colloidal platinum nanoparticles synthesized in the 1-4 nm size range. The nanoparticles were prepared via a solution-based method in which the size could be controlled by varying reaction conditions, such as the alcohol used as the reductant. Poly(vinylpyrrolidone), or PVP, (MW = 29,000 g/mol) was employed as a capping agent to stabilize the synthesized nanoparticles in solution. A model for determining the size of the metallic nanoparticle core from MALDI-TOF mass spectra has been developed and verified through correlation with particle sizes from transmission electron microscopy (TEM) and X-ray diffraction (XRD) measurements. In this model it was assumed that 1.85 nm nanoparticles are capped by one PVP chain, which was verified through experiments performed with capped and uncapped nanoparticles. Larger nanoparticles are capped by either two (2.60 and 2.94 nm) or three (3.69 nm) PVP chains. These findings clearly indicate the usefulness of MALDI-TOF MS as a technique for fully characterizing nanoscale materials in order to elucidate structure-property relationships.
Navin, Jason K.; Grass, Michael E.; Somorjai, Gabor A.; Marsh, Anderson L.
Facilities: NHMFL 9.4 Tesla Fourier Transform Ion Cyclotron Resonance Mass Spectrometer Citation: Characterization of Pine Pellet and Peanut Hull Pyrolysis of Bio-Oils by Negative-Ion Electrospray Ionization Fourier
with greater than 1% relative abundance in either phase are shown. Pyrolysis of solid biomass, in this case: Characterization of Pine Pellet and Peanut Hull Pyrolysis of Bio-Oils by Negative-Ion Electrospray Ionization of nitrogen-containing species identified in the peanut hull pyrolysis oil by FT-ICR mass spectrometry
Trace elements in coal by glow discharge mass spectrometry
A need and a demand exist for determining trace elements in coal and coal related by-products, especially those elements which may potentially be a health hazard. The provisions of the 1990 clean air act require that the EPA evaluate the emissions of electric utilities for trace elements and other potentially hazardous organic compounds. The coal fired electric utility industry supplies roughly 60% of the total generating capacity of 2,882,525 million kilowatt hours (nearly 3 trillion kilowatt hours) generated in the U.S. This is accomplished by 414 power plants scattered across the country that burned 813,508,000 short tons of coal in 1993. The relative volatility of some inorganic constituents in coal makes them more prone to be emitted to the atmosphere following combustion. The production of analytical data for trace elements is known to be a difficult task in coal and by-products of coal combustion (fly ash, bottom ash, gas streams, etc.), in terms of both sample collection and analytical determinations. There are several common analytical methods available to the analyst to determine trace elements in coal and coal by-products. In general analytical germs, the material to be analyzed can be totally solubilized (or extracted), or the elements analytes can be determined in the material as a solid. A relatively new elemental technique, Glow Discharge Mass Spectrometry (GDMS) can be used with solids as well. This new analytical technique had never before been applied directly to coal. The radio frequency-glow discharge quadropole mass spectrometer was used to analyze coal directly for the first time ever by rf-GDMS. The rf-GDMS technique is described.
Jacobs, M.L.; Wilson, C.R.; Pestovich, J. Jr. [WAL Inc., Wheat Ridge, CO (United States)] [and others
The Department of Energy (DOE) National Nuclear Security Administration (NNSA) has a specialized need for analyzing low mass gas species at very high resolutions. The currently preferred analytical method is electromagnetic sector mass spectrometry. This method allows the NNSA Nuclear Security Enterprise (NSE) to resolve species of similar masses down to acceptable minimum detection limits (MDLs). Some examples of these similar masses are helium-4/deuterium and carbon monoxide/nitrogen. Through the 1980s and 1990s, there were two vendors who supplied and supported these instruments. However, with declining procurements and down turns in the economy, the supply of instruments, service and spare parts from these vendors has become less available, and in some cases, nonexistent. The largest NSE user of this capability is the Savannah River Site (SRS), located near Aiken, South Carolina. The Research and Development Engineering (R&DE) Group in the Savannah River National Laboratory (SRNL) investigated the areas of instrument support that were needed to extend the life cycle of these aging instruments. Their conclusions, as to the focus areas of electromagnetic sector mass spectrometers to address, in order of priority, were electronics, software and hardware. Over the past 3-5 years, the R&DE Group has designed state of the art electronics and software that will allow high resolution legacy mass spectrometers, critical to the NNSA mission, to be operated for the foreseeable future. The funding support for this effort has been from several sources, including the SRS Defense Programs, NNSA Readiness Campaign, Pantex Plant and Sandia National Laboratory. To date, electronics systems have been upgraded on one development system at SRNL, two production systems at Pantex and one production system at Sandia National Laboratory. An NSE working group meets periodically to review strategies going forward. The R&DE Group has also applied their work to the electronics for a Thermal Ionization Mass Spectrometer (TIMS) instrument, which applies a similar mass spectrometric technology for resolving high mass isotopes, such as plutonium and uranium. Due to non-compete clauses for DOE, all work has been performed and applied to instruments which are obsolete and are no longer supported by the original vendor.
Wyrick, S.; Cordaro, J.; Reeves, G.; Mcintosh, J.; Mauldin, C.; Tietze, K.; Varble, D.
Fractal morphology, imaging and mass spectrometry of single aerosol particles in flight (CXIDB ID 16)
DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]
This deposition includes the aerosol diffraction images used for phasing, fractal morphology, and time-of-flight mass spectrometry. Files in this deposition are ordered in subdirectories that reflect the specifics.
Loh, N. Duane
Development of Advanced Optics and High Resolution Instrumentation for Mass Spectrometry Based Proteomics
Imaging mass spectrometry (MS) analysis allows scientists the ability to obtain spatial and chemical information of analytes on a wide variety of surfaces. The ability to image biological analytes is an important tool in many areas of life science...
Sherrod, Stacy D.
Measurements of Volatile Organic Compounds Using Proton Transfer Reaction - Mass Spectrometry during the MILAGRO 2006 Campaign
Volatile organic compounds (VOCs) were measured by proton transfer reaction � mass spectrometry (PTR-MS) on a rooftop in the urban mixed residential and industrial area North Northeast of downtown Mexico City as part of ...
Fortner, E. C.
Matrix effects in inductively coupled plasma mass spectrometry
The inductively coupled plasma is an electrodeless discharge in a gas (usually Ar) at atmospheric pressure. Radio frequency energy generated by a RF power source is inductively coupled to the plasma gas through a water cooled load coil. In ICP-MS the {open_quotes}Fassel{close_quotes} TAX quartz torch commonly used in emission is mounted horizontally. The sample aerosol is introduced into the central flow, where the gas kinetic temperature is about 5000 K. The aerosol is vaporized, atomized, excited and ionized in the plasma, and the ions are subsequently extracted through two metal apertures (sampler and skimmer) into the mass spectrometer. In ICP-MS, the matrix effects, or non-spectroscopic interferences, can be defined as the type of interferences caused by dissolved concomitant salt ions in the solution. Matrix effects can be divided into two categories: (1) signal drift due to the deposition of solids on the sampling apertures; and/or (2) signal suppression or enhancement by the presence of the dissolved salts. The first category is now reasonably understood. The dissolved salts, especially refractory oxides, tend to deposit on the cool tip of the sampling cone. The clogging of the orifices reduces the ion flow into the ICP-MS, lowers the pressure in the first stage of ICP-MS, and enhances the level of metal oxide ions. Because the extent of the clogging increases with the time, the signal drifts down. Even at the very early stage of the development of ICP-MS, matrix effects had been observed. Houk et al. found out that the ICP-MS was not tolerant to solutions containing significant amounts of dissolved solids.
Chen, Xiaoshan
SwePep, a Database Designed for Endogenous Peptides and Mass Spectrometry*
SwePep, a Database Designed for Endogenous Peptides and Mass Spectrometry* Maria Fa� lth�, Karl Sko� ld�, Mathias Norrman, Marcus Svensson�, David Fenyo� , and Per E. Andren�** A new database, Swe the experimental peptide masses are compared with the peptide masses stored in the database both with and without
Chait, Brian T.
Plasma desorption mass spectrometry of organics at low temperatures
The desorption/ionization of volatile hydrocarbons by Plasma Desorption (PD) produces a series of molecular ions. Among these are deprotonated molecular ions, which are not usually observed in PD. The H-loss phenomenon was examined as a function...
Shirey, Eldon Lynn
A new method that allows rapid preconcentration and separation of plutonium and neptunium in water samples was developed for the measurement of {sup 237}Np and Pu isotopes by inductively-coupled plasma mass spectrometry (ICP-MS) and alpha spectrometry; a hybrid approach. {sup 238}U can interfere with {sup 239}Pu measurement by ICP-MS as {sup 238}UH{sup +} mass overlap and {sup 237}Np via peak tailing. The method provide enhanced removal of uranium by separating Pu and Np initially on TEVA Resin, then moving Pu to DGA resin for additional removal of uranium. The decontamination factor for uranium from Pu is almost 100,000 and the decontamination factor for U from Np is greater than 10,000. This method uses stacked extraction chromatography cartridges and vacuum box technology to facilitate rapid separations. Preconcentration is performed using a streamlined calcium phosphate precipitation method. Purified solutions are split between ICP-MS and alpha spectrometry so that long and short-lived Pu isotopes can be measured successfully. The method allows for simultaneous extraction of 20 samples (including QC samples) in 4 to 6 hours, and can also be used for emergency response. {sup 239}Pu, {sup 242}Pu and {sup 237}Np were measured by ICP-MS, while {sup 236}Pu, {sup 238}Pu, and {sup 239}Pu were measured by alpha spectrometry.
Maxwell, S.; Jones, V.; Culligan, B.; Nichols, S.; Noyes, G.
A Mass Spectrometry Study of Isotope Separation in the Laser Plume
Gamma Ray Spectrometry . . . . . . . . . . . . . . . . . . .29, 30] Gamma Ray Spectrometry Gamma ray spectrometry willare measured by gamma spectrometry and compared to model
Suen, Timothy Wu
Laser Ablation Sampling of Materials Directly into the Formed Liquid Microjunction of a Continuous Flow Surface Sampling Probe/Electrospray Ionization Emitter for Mass Spectral Analysis and Imaging
Transmission geometry laser ablation directly into a formed liquid microjunction of a continuous flow liquid microjunction surface sampling probe/electrospray ionization emitter was utilized for molecular and elemental detection and mass spectrometry imaging. The ability to efficiently capture and ionize ablated material was demonstrated by the detection of various small soluble n-mers of polyaniline and silver ion solvent clusters formed from laser ablation of electropolymerized polyaniline and silver thin films, respectively. In addition, analysis of surfaces that contain soluble components was accomplished by coating or laminating the sample with an insoluble film to enable liquid junction formation without directly extracting material from the surface. The ability to perform mass spectrometry imaging at a spatial resolution of about 50 m was illustrated by using laminated inked patterns on a microscope slide. In general, these data demonstrate at least an order of magnitude signal enhancement compared to the non-contact, laser ablation droplet capture-based surface sampling/ionization approaches that have been previously presented.
Ovchinnikova, Olga S [ORNL] [ORNL; Lorenz, Matthias [ORNL] [ORNL; Kertesz, Vilmos [ORNL] [ORNL; Van Berkel, Gary J [ORNL] [ORNL
Spatial Querying of Imaging Mass Spectrometry Data for the Biochemical Characterization of Anatomical Regions in Tissue
Spatial Querying of Imaging Mass Spectrometry Data for the Biochemical Characterization tissue section. In this paper we develop methods that enable spatial querying of MSI data. The objective that adds spatial information to mass spectral biochemical analysis. It delivers insight into the spatial
International Journal of Mass Spectrometry 219 (2002) 7377 Protein charge transport in gas phase
temperature limit, the rotational energy can be transferred with very high efficiency and hence one obtainsInternational Journal of Mass Spectrometry 219 (2002) 7377 Protein charge transport in gas phase high charge transport efficiency. (Int J Mass Spectrom 219 (2002) 7377) © 2002 Elsevier Science B
Sheu, Sheh-Yi
Formation of iron complexs from trifluoroacetic acid based liquid chromatography mobile phases as interference ions in liquid chromatography/electrospray ionization mass spectrometric analysis
Two unexpected singly charged ions at m/z 1103 and 944 have been observed in mass spectra obtained from electrospray ionization-mass spectrometric analysis of liquid chromatography effluents with mobile phases containing trifluoroacetic acid. Accurate mass measurement and tandem mass spectrometry studies revealed that these two ions are not due to any contamination from solvents and chemicals used for mobile and stationary phases or from the laboratory atmospheric environment. Instead these ions are clusters of trifluoroacetic acid formed in association with acetonitrile, water and iron from the stainless steel union used to connect the column with the electrospray tip and to apply high voltage; the molecular formulae are Fe+((OH)(H2O)2)9(CF3COOH)5 and Fe+((OH)(H2O)2)6 (CF3COOH)5.
Shukla, Anil K.; Zhang, Rui; Orton, Daniel J.; Zhao, Rui; Clauss, Therese RW; Moore, Ronald J.; Smith, Richard D.
The formation of massive stars exceeding 10 M {sub Sun} usually results in large-scale molecular outflows. Numerical simulations, including ionization, of the formation of such stars show evidence for ionization-driven molecular outflows. Here we examine whether the outflows seen in these models reproduce the observations. We compute synthetic ALMA and CARMA maps of CO emission lines of the outflows, and compare their signatures to existing single-dish and interferometric data. We find that the ionization-driven models can only reproduce weak outflows around high-mass star-forming regions. We argue that expanding H II regions probably do not represent the dominant mechanism for driving observed outflows. We suggest instead that observed outflows are driven by the collective action of the outflows from the many lower-mass stars that inevitably form around young massive stars in a cluster.
Peters, Thomas; Klessen, Ralf S. [Institut fuer Theoretische Astrophysik, Universitaet Heidelberg, Zentrum fuer Astronomie, Albert-Ueberle-Str. 2, D-69120 Heidelberg (Germany); Klaassen, Pamela D. [European Southern Observatory, Karl-Schwarzschild-Strasse 2, D-85748 Garching (Germany); Mac Low, Mordecai-Mark [Department of Astrophysics, American Museum of Natural History, 79th Street at Central Park West, New York, NY 10024-5192 (United States); Banerjee, Robi, E-mail: email@example.com [Hamburger Sternwarte, Gojenbergsweg 112, D-21029 Hamburg (Germany)
In situ UPb dating of micro-baddeleyite by secondary ion mass spectrometry Axel K. Schmitt a,
In situ UPb dating of micro-baddeleyite by secondary ion mass spectrometry Axel K. Schmitt a secondary ion mass spectrometry (SIMS) in situ analysis of ng-mass crystals that cannot be efficiently conventional mineral separation methods are not optimized for recovery of such small grains, techniques
B American Society for Mass Spectrometry, 2012 DOI: 10.1007/s13361-012-0404-0
pI, mobile phase pH) [12], ion suppression of co-eluting analytes [13], and mobile phase flow rateB American Society for Mass Spectrometry, 2012 DOI: 10.1007/s13361-012-0404-0 J. Am. Soc. Mass Improves Peptide Identification by Tandem Mass Spectrometry Jesse G. Meyer, Elizabeth A. Komives Department
Komives, Elizabeth A.
Laser Desorption Single-Photon Ionization of Asphaltenes: Mass Range, Compound Sensitivity, and Matrix Effects
Laser Desorption Single-Photon Ionization of Asphaltenes: Mass Range, Compound Sensitivity-level characterization of petroleum asphaltenes is important for addressing reservoir concerns such as connectivity as a favored technique for asphaltene analysis, because of its ability to detect these samples with minimal
Zare, Richard N.
Identification of serum biomarkers for occupational medicamentosa-like dermatitis induced by trichloroethylene using mass spectrometry
Occupational medicamentosa-like dermatitis induced by trichloroethylene (OMLDT) is an autoimmune disease and it has become a serious occupational health hazard. In the present study, we collected fasting blood samples from patients with OMLDT (n = 18) and healthy volunteers (n = 33) to explore serum peptidome patterns. Peptides in sera were purified using weak cation exchange magnetic beads (MB-WCX), and analyzed by matrix-assisted laser desorption ionization time-of-flight-mass spectrometry (MALDI-TOF-MS) and ClinProTools bioinformatics software. The intensities of thirty protein/peptide peaks were significantly different between the healthy control and OMLDT patients. A pattern of three peaks (m/z 2106.3, 2134.5, and 3263.67) was selected for supervised neural network (SNN) model building to separate the OMLDT patients from the healthy controls with a sensitivity of 95.5% and a specificity of 73.8%. Furthermore, two peptide peaks of m/z 4091.61 and 4281.69 were identified as fragments of ATP-binding cassette transporter family A member 12 (ABCA12), and cationic trypsinogen (PRRS1), respectively. Our findings not only show that specific proteomic fingerprints in the sera of OMLDT patients can be served as a differentiated tool of OMLDT patients with high sensitivity and high specificity, but also reveal the novel correlation between OMLDT with ABC transports and PRRS1, which will be of potential value for clinical and mechanistic studies of OMLDT. - Highlights: � Identify 30 differential protein/peptide peaks between OMLDT and healthy control � The test sensitivity and test specificity were 95.5% and 73.8%, respectively. � ABCA12 and PRSS1 were identified as potential biomarkers in OMLDT patients.
Hong, Wen-Xu; Liu, Wei [Key Laboratory of Modern Toxicology of Shenzhen, Medical Key Laboratory of Guangdong Province, Medical Key Laboratory of Health Toxicology of Shenzhen, Shenzhen Center for Disease Control and Prevention, Shenzhen 518055 (China); Zhang, Yanfang [Shenzhen Prevention and Treatment Center for Occupational Disease, Shenzhen 518001 (China); Huang, Peiwu; Yang, Xifei; Ren, Xiaohu; Ye, Jinbo; Huang, Haiyan [Key Laboratory of Modern Toxicology of Shenzhen, Medical Key Laboratory of Guangdong Province, Medical Key Laboratory of Health Toxicology of Shenzhen, Shenzhen Center for Disease Control and Prevention, Shenzhen 518055 (China); Tang, Haiyan [Shenzhen Prevention and Treatment Center for Occupational Disease, Shenzhen 518001 (China); Zhou, Guifeng [Medical School of Hunan Normal University, Changsha 410006 (China); Huang, Xinfeng; Zhuang, Zhixiong [Key Laboratory of Modern Toxicology of Shenzhen, Medical Key Laboratory of Guangdong Province, Medical Key Laboratory of Health Toxicology of Shenzhen, Shenzhen Center for Disease Control and Prevention, Shenzhen 518055 (China); Liu, Jianjun, E-mail: email@example.com [Key Laboratory of Modern Toxicology of Shenzhen, Medical Key Laboratory of Guangdong Province, Medical Key Laboratory of Health Toxicology of Shenzhen, Shenzhen Center for Disease Control and Prevention, Shenzhen 518055 (China)
Apparatus and methods for continuous beam fourier transform mass spectrometry
A continuous beam Fourier transform mass spectrometer in which a sample of ions to be analyzed is trapped in a trapping field, and the ions in the range of the mass-to-charge ratios to be analyzed are excited at their characteristic frequencies of motion by a continuous excitation signal. The excited ions in resonant motions generate real or image currents continuously which can be detected and processed to provide a mass spectrum.
McLuckey, Scott A. (Oak Ridge, TN); Goeringer, Douglas E. (Oak Ridge, TN)
A new rapid separation method that allows separation and preconcentration of actinides in urine samples was developed for the measurement of longer lived actinides by inductively coupled plasma mass spectrometry (ICP-MS) and short-lived actinides by alpha spectrometry; a hybrid approach. This method uses stacked extraction chromatography cartridges and vacuum box technology to facilitate rapid separations. Preconcentration, if required, is performed using a streamlined calcium phosphate precipitation. Similar technology has been applied to separate actinides prior to measurement by alpha spectrometry, but this new method has been developed with elution reagents now compatible with ICP-MS as well. Purified solutions are split between ICP-MS and alpha spectrometry so that long- and short-lived actinide isotopes can be measured successfully. The method allows for simultaneous extraction of 24 samples (including QC samples) in less than 3 h. Simultaneous sample preparation can offer significant time savings over sequential sample preparation. For example, sequential sample preparation of 24 samples taking just 15 min each requires 6 h to complete. The simplicity and speed of this new method makes it attractive for radiological emergency response. If preconcentration is applied, the method is applicable to larger sample aliquots for occupational exposures as well. The chemical recoveries are typically greater than 90%, in contrast to other reported methods using flow injection separation techniques for urine samples where plutonium yields were 70-80%. This method allows measurement of both long-lived and short-lived actinide isotopes. 239Pu, 242Pu, 237Np, 243Am, 234U, 235U and 238U were measured by ICP-MS, while 236Pu, 238Pu, 239Pu, 241Am, 243Am and 244Cm were measured by alpha spectrometry. The method can also be adapted so that the separation of uranium isotopes for assay is not required, if uranium assay by direct dilution of the urine sample is preferred instead. Multiple vacuum box locations may be set-up to supply several ICP-MS units with purified sample fractions such that a high sample throughput may be achieved, while still allowing for rapid measurement of short-lived actinides by alpha spectrometry.
Maxwell, S.; Jones, V.
Development of Soft Ionization for Particulate Organic Detection with the Aerodyne Aerosol Mass Spectrometer
During this DOE SBIR Phase II project, we have successfully developed several soft ionization techniques, i.e., ionization schemes which involve less fragmentation of the ions, for use with the Aerodyne time-of-flight aerosol mass spectrometer (ToF-AMS). Vacuum ultraviolet single photon ionization was demonstrated in the laboratory and deployed in field campaigns. Vacuum ultraviolet single photon ionization allows better identification of organic species in aerosol particles as shown in laboratory experiments on single component particles, and in field measurements on complex multi-component particles. Dissociative electron attachment with lower energy electrons (less than 30 eV) was demonstrated in the measurement of particulate organics in chamber experiments in Switzerland, and is now a routine approach with AMS systems configured for bipolar, negative ion detection. This technique is particularly powerful for detection of acidic and other highly oxygenated secondary organic aerosol (SOA) chemical functionality. Low energy electron ionization (10 to 12 eV) is also a softer ionization approach routinely available to AMS users. Finally, Lithium ion attachment has been shown to be sensitive to more alkyl-like chemical functionality in SOA. Results from Mexico City are particularly exciting in observing changes in SOA molecular composition under different photochemical/meteorological conditions. More recent results detecting biomass burns at the Montana fire lab have demonstrated quantitative and selective detection of levoglucosan. These soft ionization techniques provide the ToF-AMS with better capability for identifying organic species in ambient atmospheric aerosol particles. This, in turn, will allow more detailed study of the sources, transformations and fate of organic-containing aerosol.
Trimborn, A; Williams, L R; Jayne, J T; Worsnop, D R
Examination of the rate of peptide biosynthesis in neuroendocrine cell lines using a stable isotopic label and mass spectrometry
isotopic label and mass spectrometry Fa-Yun Che,*,1 Quan Yuan,* ,1 Elena Kalinina* and Lloyd D. Fricker-Leu) and used mass spectrometry to measure the biosynthetic rate of c-lipotropin in the AtT-20 cell lines. Keywords: carboxypeptidase, gamma-lipotropin, insulin, prohormone convertase, proinsulin
Tian, Weidong
International Journal of Mass Spectrometry 316318 (2012) 259267 Contents lists available at SciVerse ScienceDirect
International Journal of Mass Spectrometry 316�318 (2012) 259�267 Contents lists available at SciVerse ScienceDirect International Journal of Mass Spectrometry journal homepage: www.elsevier.com/locate/ijms Influence of a gamma amino acid on the structures and reactivity of peptide a3 ions Matthew C. Berniera
FOCUS: HARSH ENVIRONMENT MASS SPECTROMETRY Field Testing of Lake Water Chemistry with a
FOCUS: HARSH ENVIRONMENT MASS SPECTROMETRY Field Testing of Lake Water Chemistry with a Portable waters. KOALA is a backpackable MS operated from above the water surface, in which samples are pumped for temperature control of a membrane inlet when steep thermal gradients are present in a water body, as well
Entekhabi, Dara
Two-Step Laser Mass Spectrometry of Asphaltenes Andrew E. Pomerantz,*,
that high pulse energy and sample concentration promote aggregation of asphaltenes in the plasma plumeTwo-Step Laser Mass Spectrometry of Asphaltenes Andrew E. Pomerantz,*, Matthew R. Hammond, Amy L- heptane, asphaltenes are a highly aromatic, polydisperse mixture consisting of the heaviest and most polar
Surface Analysis by Highly Charged Ion Based Secondary Ion Mass Spectrometry
Surface Analysis by Highly Charged Ion Based Secondary Ion Mass Spectrometry T. Schenkel,1 A high vacuum (10^8 torr). In posi- tive polarity, HCI can be decelerated to an impact energy of $1 ke in the interaction of slow (u highly charged ions (e.g., Au69+ ) with solid surfaces increases secondary
ORGANIC MASS SPECTROMETRY, VOL. 21, 193-195 (1986) Energy Deposition in [Fe(CO),] ''Upon
ORGANIC MASS SPECTROMETRY, VOL. 21, 193-195 (1986) Energy Deposition in [Fe(CO),] ''Upon Collision distributions associated with gas-phase collisional activation using both low and high ion kinetic energies, and the high internal energies accessible, make the ionlsurface collision process superior to gas
Visual Steering and Verification of Mass Spectrometry Data Factorization in Air Quality Research
quality research involves the analysis of high-dimensional single particle mass spectrometry data. We data at significantly increased speed and a higher degree of ease. Index Terms--Dimension reduction of numerical error metrics, multi-dimensional data visualization. 1 INTRODUCTION Atmospheric particles increase
Hamann, Bernd
Conformational Analysis of Disordered Proteins Using H/D Exchange Mass Spectrometry
. The application of hydrogen/deuterium exchange mass spectrometry (H/D-MS) to study IDPs is presented in this dissertation. Results that demonstrate improvements to the H/D-MS method are also presented. A thermoelectrically cooled refrigeration system was developed...
Keppel, Theodore Robert
�?�Cf-plasma desorption mass spectrometry of RNA nucleosides
~ CH5 + CH3 CH3 + CH4 ~ C2H5 + H2 Proton or hydride transfer reactions of these secondary ions with the sample molecule produce the major portion of the CI mass spectra. Because the molecular ions are formed by these chemical reactions... low, and co'1'lisional deactivation between sample fons and air molecules results in a loss of intensity and resolution for the sample ions detected. -7 The vacuum in the mass spectrometer is maintained in the 10 16 torr region by a Sargent...
Piper, Duane Gilbert
(Resonance ionization spectroscopy)
J. P. Young attended the Fifth International Symposium on Resonance Ionization Spectroscopy and presented an invited oral presentation on research he and coworkers had carried out in applying diode lasers to resonance ionization mass spectrometry. A summary of the conference is given along with an assessment of some of the presentations that the author found of interest. Young also visited Professor Marassi at the University of Camerino to present a seminar and discuss mutual interests in a new molten salt research project of the author. Some of the studies at Camerino are described. Ideas concerning the author's research that came from private discussions are also presented here.
Young, J.P.
National Centre for Biological Sciences Mass Spectrometry Facility
: Sample Information Number of samples: Sample ID: Concentration: Solubility: Expected mass (Da): Molecular: Protein Peptide Lipid Nucleic acid Others (specify) Analysis Requirement ESI MS, low resolution ESI MS, high resolution LC-ESI MS LC-ESI MS/MS Others (specify) Signature of research supervisor: Signature
Bhalla, Upinder S.
Evaluation of Hypervelocity Gold Nanoparticles for Nanovolume Surface Mass Spectrometry
in Figure VI-1 ................................................................................................ 166 VI-3 SI yields for samples containing various amounts of silver and gold on top of a PMMA film analyzed by massive gold clusters... and Bi+ ........ 169 VI-4 Negative mode mass spectrum from atomic-SIMS analysis of a PMMA surface ........................................................................................... 170 VI-5 Proposed structures for fragment ions...
DeBord, John 1986-
Explanatory Optimization of Protein Mass Spectrometry via Genetic Search
of the mass spectrometer settings that accounts for much of this success. Specifically, the conditions of Wales, Aberystwyth, Ceredigion SY23 3DD, U.K. Optimizing experimental conditions for the effective analy that little or no a priori knowledge of the optimal conditions is available. There is much current interest
Fernandez, Thomas
Electron impact and chemical ionization mass spectral analysis of a volatile uranyl derivative
Quadrupole mass spectral analysis of the volatile uranium ligand complex bis (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato) dioxouranium-di-n-butyl sulfoxide is described utilizing electron impact (EI) and methane chemical ionization (CI) ion sources. All major ions are tentatively identified and the potential usefulness of this complex for determining uranium isotope /sup 235/U//sup 238/U abundance is demonstrated.
Reutter, D.J.; Hardy, D.R.
Coulomb crystal mass spectrometry in a digital ion trap
We present a mass spectrometric technique for identifying the masses and relative abundances of Coulomb-crystallized ions held in a linear Paul trap. A digital radiofrequency waveform is employed to generate the trapping potential, as this can be cleanly switched off, and static dipolar fields subsequently applied to the trap electrodes for ion ejection. Excellent detection efficiency is demonstrated for Ca+ and CaF+ ions from bi-component Ca+/CaF+ Coulomb crystals prepared by reaction of Ca+ with CH3F. A quantitative linear relationship is observed between ion number and the corresponding integrated TOF peak, independent of the ionic species. The technique is applicable to a diverse range of multi-component Coulomb crystals - demonstrated here for Ca+/NH3+/NH4+ and Ca+/CaOH+/CaOD+ crystals - and will facilitate the measurement of ion-molecule reaction rates and branching ratios in complicated reaction systems.
Deb, Nabanita; Smith, Alexander D; Keller, Matthias; Rennick, Christopher J; Heazlewood, Brianna R; Softley, Timothy P
Ion source for high-precision mass spectrometry
The invention is directed to a method for increasing the precision of positive-ion relative abundance measurements conducted in a sector mass spectrometer having an ion source for directing a beam of positive ions onto a collimating slit. The method comprises incorporating in the source an electrostatic lens assembly for providing a positive-ion beam of circular cross section for collimation by the slit. 2 figures, 3 tables.
Todd, P.J.; McKown, H.S.; Smith, D.H.
Cadmium binding studies to the earthworm Lumbricus rubellus metallothionein by electrospray mass spectrometry and circular dichroism spectroscopy
The earthworm Lumbricus rubellus has been found to inhabit cadmium-rich soils and accumulate cadmium within its tissues. Two metallothionein (MT) isoforms (1 and 2) have been identified and cloned from L. rubellus. In this study, we address the metalation status, metal coordination, and structure of recombinant MT-2 from L. rubellus using electrospray ionization mass spectrometry (ESI-MS), UV absorption, and circular dichroism (CD) spectroscopy. This is the first study to show the detailed mass and CD spectral properties for the important cadmium-containing earthworm MT. We report that the 20-cysteine L. rubellus MT-2 binds seven Cd{sup 2+} ions. UV absorption and CD spectroscopy and ESI-MS pH titrations show a distinct biphasic demetalation reaction, which we propose results from the presence of two metal-thiolate binding domains. We propose stoichiometries of Cd{sub 3}Cys{sub 9} and Cd{sub 4}Cys{sub 11} based on the presence of 20 cysteines split into two isolated regions of the sequence with 11 cysteines in the N-terminal and 9 cysteines in the C-terminal. The CD spectrum reported is distinctly different from any other metallothionein known suggesting quite different binding site structure for the peptide.
Ngu, Thanh T. [Department of Chemistry, University of Western Ontario, London, Ont., N6A 5B7 (Canada); Sturzenbaum, Stephen R. [School of Biomedical and Health Sciences, King's College, London, SE1 9NH (United Kingdom); Stillman, Martin J. [Department of Chemistry, University of Western Ontario, London, Ont., N6A 5B7 (Canada)]. E-mail: firstname.lastname@example.com
Sampling probe for microarray read out using electrospray mass spectrometry
An automated electrospray based sampling system and method for analysis obtains samples from surface array spots having analytes. The system includes at least one probe, the probe including an inlet for flowing at least one eluting solvent to respective ones of a plurality of spots and an outlet for directing the analyte away from the spots. An automatic positioning system is provided for translating the probe relative to the spots to permit sampling of any spot. An electrospray ion source having an input fluidicly connected to the probe receives the analyte and generates ions from the analyte. The ion source provides the generated ions to a structure for analysis to identify the analyte, preferably being a mass spectrometer. The probe can be a surface contact probe, where the probe forms an enclosing seal along the periphery of the array spot surface.
Van Berkel, Gary J.
Quantitative Analysis of Tetramethylenedisulfotetramine ("Tetramine") Spiked into Beverages by Liquid Chromatography Tandem Mass Spectrometry with Validation by Gas Chromatography Mass Spectrometry
Tetramethylenedisulfotetramine, commonly known as tetramine, is a highly neurotoxic rodenticide (human oral LD{sub 50} = 0.1 mg/kg) used in hundreds of deliberate food poisoning events in China. Here we describe a method for quantitation of tetramine spiked into beverages, including milk, juice, tea, cola, and water and cleaned up by C8 solid phase extraction and liquid-liquid extraction. Quantitation by high performance liquid chromatography tandem mass spectrometry (LC/MS/MS) was based upon fragmentation of m/z 347 to m/z 268. The method was validated by gas chromatography mass spectrometry (GC/MS) operated in SIM mode for ions m/z 212, 240, and 360. The limit of quantitation was 0.10 {micro}g/mL by LC/MS/MS versus 0.15 {micro}g/mL for GC/MS. Fortifications of the beverages at 2.5 {micro}g/mL and 0.25 {micro}g/mL were recovered ranging from 73-128% by liquid-liquid extraction for GC/MS analysis, 13-96% by SPE and 10-101% by liquid-liquid extraction for LC/MS/MS analysis.
Owens, J; Hok, S; Alcaraz, A; Koester, C
Mass Spectrometry Data from the Biological MS Data and Software Distribution Center
The mass spectrometry capabilities at Pacific Northwest National Laboratory (PNNL) are primarily applied to biological research, with an emphasis on proteomics and metabolomics. Many of these cutting-edge mass spectrometry capabilities and bioinformatics methods are housed in the Department of Energy's Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility operated by PNNL. These capabilities have been developed and acquired through cooperation between the EMSL national scientific user program and PNNL programmatic research. At the website of the Biological MS Data and Software Distribution Center, the following resources are made available: PNNL-developed software tools and source code, PNNL-generated raw data and processed results, links to publications that used the data and results available on this site, and tutorials and user manuals. [taken from http://omics.pnl.gov/
Anderson, Gordon
Double-gated isolated vertically aligned carbon nanofiber field emission and field ionization arrays
Electron impact ionization (ElI) is used extensively in mass spectrometry for gas-phase analytes. Due to the significant amount of fragmentation generated by ElI, the spectrum is usually very noisy. In addition, the ...
Chen, Liang-Yu, 1979-
Analysis of a Fossil Bone from the Archaeological Settlement Malu Rosu, Romania by Accelerator Mass Spectrometry
A fossil bone from the archaeological site Malu Rosu Giurgiu, in Romania has been analyzed by accelerator mass spectrometry to estimate its age by determining its $^{14}$C content. The radiocarbon age of the bone is in agreement with the date obtained by the method for age determination, based on fluorine content. This is the first radiocarbon dating for the final Neolithic period, for this archaeological settlement in the Romanian region.
Agata Olariu; Ion V. Popescu; Ragnar Hellborg; Kristina Stenstr�m; Mikko Faarinen; Per Persson; Bengt Erlandsson; G�ran Skog; Emilian Alexandrescu
Characterization of surface and layered films with cluster secondary ion mass spectrometry
.................................... 84 1 CHAPTER I INTRODUCTION Secondary ion mass spectrometry (SIMS) is well recognized a sensitive surface analysis method [1]. It utilizes energetic charged particles (primary ions) to probe surfaces. Impacts from the high energy, high... surprisingly, the most efficient projectiles for this purpose are those depositing a high density of energy. Desorption with keV and MeV Projectiles SIMS operates in two different modes: dynamic SIMS and static SIMS. The major difference between these modes...
Li, Zhen
Real-time monitoring of volatile organic compounds using chemical ionization mass spectroscopy: Final report
Volatile organic compound (VOC) emission to the atmosphere is of great concern to semiconductor manufacturing industries, research laboratories, the public, and regulatory agencies. Some industries are seeking ways to reduce emissions by reducing VOCs at the point of use (or generation). This paper discusses the requirements, design, calibration, and use of a sampling inlet/quadrupole mass spectrometer system for monitoring VOCs in a semiconductor manufacturing production line. The system uses chemical ionization to monitor compounds typically found in the lithography processes used to manufacture semiconductor devices (e.g., acetone, photoresist). The system was designed to be transportable from tool to tool in the production line and to give the operator real-time feedback so the process(es) can be adjusted to minimize VOC emissions. Detection limits ranging from the high ppb range for acetone to the low ppm range fore other lithography chemicals were achieved using chemical ionization mass spectroscopy at a data acquisition rate of approximately 1 mass spectral scan (30 to 200 daltons) per second. A demonstration of exhaust VOC monitoring was performed at a working semiconductor fabrication facility during actual wafer processing.
Thornberg, S.M.; Mowry, C.D.; Keenan, M.R.; Bender, S.F.A. [Sandia National Labs., Albuquerque, NM (United States). Gas Analysis Lab.; Owen, T. [Intel Corp., Rio Rancho, NM (United States)
2?52Cf plasma desorption mass spectrometry of metal clusters
August 1991 Major Subject: Chemistry s Cf PLASMA DESORPTION MASS SPECTROMETRY OF METAL CLUSTERS A Thesis by JANITA MURIEL HUGHES Approved as to style and content by: R. D. ac ane (Chair of Co 'uee) J. P. Fac er (Member) A. . aray (Member) M... and negative ion spectra. However, close-packed complexes like [Pt (CO), g" form cluster cor- responding to the oligomeric species, [(Pt ), (CO)?], from n=2 to n=20. The latter structure contains 520 platinum atoms with an observed mass in excess of m/z 100...
Hughes, Janita Muriel
Statistical Methods for the Analysis of Mass Spectrometry-based Proteomics Data
. This research is supported by the. This work was sponsored by a subcontract from PNNL and by the NIH R25-CA-90301 training grant at TAMU. Additional support was provided by KAUST-IAMCS Innovation grant, by NIH grant DK070146 and by the National Institute...-MS Liquid chromatographyCMass spectrometry M/Z Mass over charge ratio NET Normalized elution time NMC Number of missed cleavage sites NTE Number of tryptic ends PEP Posterior error probability PM Potential matches PMF Probability mass function PNNL...
Wang, Xuan
Automatic Gain Control in Mass Spectrometry using a Jet Disrupter Electrode in an Electrodynamic Ion Funnel
We report on the use of a jet disrupter electrode in an electrodynamic ion funnel as an electronic valve to regulate the intensity of the ion beam transmitted through the interface of a mass spectrometer in order to perform automatic gain control (AGC). The ion flux is determined by either directly detecting the ion current on the conductance limiting orifice of the ion funnel or using a short mass spectrometry acquisition. Based upon the ion flux intensity, the voltage of the jet disrupter is adjusted to alter the transmission efficiency of the ion funnel to provide a desired ion population to the mass analyzer. Ion beam regulation by an ion funnel is shown to provide an unbiased control to within a few percent of a targeted ion intensity or abundance. The utility of ion funnel AGC was evaluated using a protein tryptic digest analyzed with liquid chromatography Fourier transform ion cyclotron resonance (LC-FTICR) mass spectrometry. The ion population in the ICR cell was accurately controlled to a variety of different levels, which improved data quality and provided better mass measurement accuracy.
Page, Jason S.; Bogdanov, Bogdan; Vilkov, Andrey N.; Prior, David C.; Buschbach, Michael A.; Tang, Keqi; Smith, Richard D.
Electrospray mass spectrometry of NeuAc oligomers associated with the C fragment of the tetanus toxin
The Clostridial neurotoxins, botulinum and tetanus, gain entry into neuronal cells by protein recognition involving cell specific binding sites. The sialic or N-acetylneuraminic acid (NeuAc) residues of gangliosides attached to the surface of motor neurons are the suspected recognition and interaction points with Clostridial neurotoxins, although not necessarily the only ones. We have used electrospray ionization mass spectrometry (ESIMS) to examine formation of complexes between the tetanus toxin C fragment, or targeting domain, and carbohydrates containing NeuAc groups to determine how NeuAc residues contribute to ganglioside binding. ESI-MS was used to rapidly and efficiently measure dissociation constants for a number of related NeuAc-containing carbohydrates and NeuAc oligomers, information that has helped identify the structural features of gangliosides that determine their binding to tetanus toxin. The strength of the interactions between the C fragment and (NeuAc){sub n}, are consistent with the topography of the targeting domain of tetanus toxin and the nature of its carbohydrate binding sites. The results suggest that the targeting domain of tetanus toxin contains two binding sites that can accommodate NeuAc (or a dimer). This study also shows that NeuAc must play an important role in ganglioside binding and molecular recognition, a process critical for normal cell function and one frequently exploited by toxins, bacteria and viruses to facilitate their entrance into cells.
Prieto, M C; Whittal, R M; Baldwin, M A; Burlingame, A L; Balhorn, R
Time-of-flight secondary ion mass spectrometry with transmission of energetic primary cluster ions through foil targets
We developed time-of-flight (TOF) secondary ion (SI) mass spectrometry that provides informative SI ion mass spectra without needing a sophisticated ion beam pulsing system. In the newly developed spectrometry, energetic large cluster ions with energies of the order of sub MeV or greater are used as primary ions. Because their impacts on the target surface produce high yields of SIs, the resulting SI mass spectra are informative. In addition, the start signals necessary for timing information on primary ion incidence are provided by the detection signals of particles emitted from the rear surface of foil targets upon transmission of the primary ions. This configuration allows us to obtain positive and negative TOF SI mass spectra without pulsing system, which requires precise control of the primary ions to give the spectra with good mass resolution. We also successfully applied the TOF SI mass spectrometry with energetic cluster ion impacts to the chemical structure characterization of organic thin film targets.
Hirata, K., E-mail: firstname.lastname@example.com [National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565 (Japan); Saitoh, Y.; Chiba, A.; Yamada, K.; Matoba, S.; Narumi, K. [Takasaki Advanced Radiation Research Institute (TARRI), Japan Atomic Energy Agency (JAEA), Takasaki, Gumma 370-1292 (Japan)] [Takasaki Advanced Radiation Research Institute (TARRI), Japan Atomic Energy Agency (JAEA), Takasaki, Gumma 370-1292 (Japan)
Schumann, K. Wendt, B. Bushaw, High-resolution triple-resonancefrom Schumann, et al. is the lack of a sharp resonance atresonance marked with an asterisk is described in the text. (Reproduced from Schumann,
Isselhardt, Brett Hallen
An Analysis of Nuclear Fuel Burnup in the AGR 1 TRISO Fuel Experiment Using Gamma Spectrometry, Mass Spectrometry, and Computational Simulation Techniques
AGR 1 was the first in a series of experiments designed to test US TRISO fuel under high temperature gas-cooled reactor irradiation conditions. This experiment was irradiated in the Advanced Test Reactor (ATR) at Idaho National Laboratory (INL) and is currently undergoing post irradiation examination (PIE) at INL and Oak Ridge National Laboratory. One component of the AGR 1 PIE is the experimental evaluation of the burnup of the fuel by two separate techniques. Gamma spectrometry was used to non destructively evaluate the burnup of all 72 of the TRISO fuel compacts that comprised the AGR 1 experiment. Two methods for evaluating burnup by gamma spectrometry were developed, one based on the Cs 137 activity and the other based on the ratio of Cs 134 and Cs 137 activities. Burnup values determined from both methods compared well with the values predicted from simulations. The highest measured burnup was 20.1 %FIMA for the direct method and 20.0 %FIMA for the ratio method (compared to 19.56% FIMA from simulations). An advantage of the ratio method is that the burnup of the cylindrical fuel compacts can determined in small (2.5 mm) axial increments and an axial burnup profile can be produced. Destructive chemical analysis by inductively coupled mass spectrometry (ICP MS) was then performed on selected compacts that were representative of the expected range of fuel burnups in the experiment to compare with the burnup values determined by gamma spectrometry. The compacts analyzed by mass spectrometry had a burnup range of 19.3 % FIMA to 10.7 % FIMA. The mass spectrometry evaluation of burnup for the four compacts agreed well with the gamma spectrometry burnup evaluations and the expected burnup from simulation. For all four compacts analyzed by mass spectrometry, the maximum range in the three experimentally determined values and the predicted value was 6% or less. The results confirm the accuracy of the nondestructive burnup evaluation from gamma spectrometry for TRISO fuel compacts across a burnup range of approximately 10 to 20 % FIMA and also validate the approach used in the physics simulation of the AGR 1 experiment.
Jason M. Harp; Paul A. Demkowicz; Phillip L. Winston; James W. Sterbentz
Multielement ultratrace analysis of molybdenum with high performance secondary ion mass spectrometry
Electron beam melting has been used to obtain ultrapure refractory metals that are gaining importance in metal oxide semiconductor--very large scale integration (MOS--VLSI) processing technology, fusion reactor technology, or as superconducting materials. Although the technology of electron beam melting is well established in the field of production of very clean refractory metals, little is known about the limitations of the method because the impurity level of the final products is frequently below the detection power of common methods for trace analysis. Characterization of these materials can be accomplished primarily by in situ methods like neutron activation analysis and mass spectrometric methods (glow discharge mass spectrometry (GDMS), secondary ion mass spectrometry (SIMS)). A suitable method for quantitative multielement ultratrace bulk analysis of molybdenum with SIMS has been developed. Detection limits of the analyzed elements from 10/sup -7/ g/g down to 10/sup -12/ g/g have been found. Additional information about the distribution of the trace elements has been accumulated.
Virag, A.; Friedbacher, G.; Grasserbauer, M.; Ortner, H.M.; Wilhartitz, P.
Analytical Validation of Accelerator Mass Spectrometry for Pharmaceutical Development: the Measurement of Carbon-14 Isotope Ratio.
Accelerator mass spectrometry (AMS) is an isotope based measurement technology that utilizes carbon-14 labeled compounds in the pharmaceutical development process to measure compounds at very low concentrations, empowers microdosing as an investigational tool, and extends the utility of {sup 14}C labeled compounds to dramatically lower levels. It is a form of isotope ratio mass spectrometry that can provide either measurements of total compound equivalents or, when coupled to separation technology such as chromatography, quantitation of specific compounds. The properties of AMS as a measurement technique are investigated here, and the parameters of method validation are shown. AMS, independent of any separation technique to which it may be coupled, is shown to be accurate, linear, precise, and robust. As the sensitivity and universality of AMS is constantly being explored and expanded, this work underpins many areas of pharmaceutical development including drug metabolism as well as absorption, distribution and excretion of pharmaceutical compounds as a fundamental step in drug development. The validation parameters for pharmaceutical analyses were examined for the accelerator mass spectrometry measurement of {sup 14}C/C ratio, independent of chemical separation procedures. The isotope ratio measurement was specific (owing to the {sup 14}C label), stable across samples storage conditions for at least one year, linear over 4 orders of magnitude with an analytical range from one tenth Modern to at least 2000 Modern (instrument specific). Further, accuracy was excellent between 1 and 3 percent while precision expressed as coefficient of variation is between 1 and 6% determined primarily by radiocarbon content and the time spent analyzing a sample. Sensitivity, expressed as LOD and LLOQ was 1 and 10 attomoles of carbon-14 (which can be expressed as compound equivalents) and for a typical small molecule labeled at 10% incorporated with {sup 14}C corresponds to 30 fg equivalents. AMS provides an sensitive, accurate and precise method of measuring drug compounds in biological matrices.
Keck, B D; Ognibene, T; Vogel, J S
Method Development of Characterization of N-linked Glycoproteins in Mass Spectrometry
in the instruments used in my research. I would also like to thank Dr. Barton F. Haynes, Dr. Hua-Xin Liao, and Laura L. Sutherland at Duke Human Vaccine Research Institute (Duke University, Durham, NC) for supplying HIV Env proteins for my research. I warmly thank...����������������������������...115 V. Determination of disulfide bond arrangement of HIV Env protein CON-S gp140 ?CFI by LC/ESI-FTICR mass spectrometry. 5.1. Introduction����������������������������120 5.2. Experimental section�����������������������...124 5.3. Results...
Zhang, Ying
230Th-234U Age-Dating Uranium by Mass Spectrometry
This is the standard operating procedure used by the Isotope Ratio Mass Spectrometry Group of the Chemical Sciences Division at LLNL for the preparation of a sample of uranium oxide or uranium metal for {sup 230}Th-{sup 234}U age-dating. The method described here includes the dissolution of a sample of uranium oxide or uranium metal, preparation of a secondary dilution, spiking of separate aliquots for uranium and thorium isotope dilution measurements, and purification of uranium and thorium aliquots for mass spectrometry. This SOP may be applied to uranium samples of unknown purity as in a nuclear forensic investigation, and also to well-characterized samples such as, for example, U{sub 3}O{sub 8} and U-metal certified reference materials. The sample of uranium is transferred to a quartz or PFA vial, concentrated nitric acid is added and the sample is heated on a hotplate at approximately 100 C for several hours until it dissolves. The sample solution is diluted with water to make the solution approximately 4 M HNO{sub 3} and hydrofluoric acid is added to make it 0.05 M HF. A secondary dilution of the primary uranium solution is prepared. Separate aliquots for uranium and thorium isotope dilution measurements are taken and spiked with {sup 233}U and {sup 229}Th, respectively. The spiked aliquot for uranium isotope dilution analysis is purified using EiChrom UTEVA resin. The spiked aliquot for thorium isotope dilution analysis is purified by, first, a 1.8 mL AG1x8 resin bed in 9 M HCl on which U adsorbs and Th passes through; second, adsorbing Th on a 1 mL AG1x8 resin bed in 8 M HNO{sub 3} and then eluting it with 9 M HCl followed by 0.1 M HCl + 0.005 M HF; and third, by passing the Th through a final 1.0 mL AG1x8 resin bed in 9 M HCl. The mass spectrometry is performed using the procedure 'Th and U Mass Spectrometry for {sup 230}Th-{sup 234}U Age Dating'.
Williams, R W; Gaffney, A M
Chemical oxidation of tryptic digests to improve sequence coverage in peptide mass fingerprint protein identification
Peptide mass fingerprinting (PMF) of protein digests is a widely-accepted method for protein identification in MS-based proteomic studies. Matrix-assisted laser desorption/ionization mass spectrometry (MALDI) is the technique of choice in PMF...
Lucas, Jessica Elaine
Ultra-high-mass mass spectrometry with charge discrimination using cryogenic detectors
An ultra-high-mass time-of-flight mass spectrometer using a cryogenic particle detector as an ion detector with charge discriminating capabilities. Cryogenic detectors have the potential for significantly improving the performance and sensitivity of time-of-flight mass spectrometers, and compared to ion multipliers they exhibit superior sensitivity for high-mass, slow-moving macromolecular ions and can be used as "stop" detectors in time-of-flight applications. In addition, their energy resolving capability can be used to measure the charge state of the ions. Charge discrimination is very valuable in all time-of-flight mass spectrometers. Using a cryogenically-cooled Nb-Al.sub.2 O.sub.3 -Nb superconductor-insulator-superconductor (SIS) tunnel junction (STJ) detector operating at 1.3 K as an ion detector in a time-of-flight mass spectrometer for large biomolecules it was found that the STJ detector has charge discrimination capabilities. Since the cryogenic STJ detector responds to ion energy and does not rely on secondary electron production, as in the conventionally used microchannel plate (MCP) detectors, the cryogenic detector therefore detects large molecular ions with a velocity-independent efficiency approaching 100%.
Frank, Matthias (Berkeley, CA); Mears, Carl A. (Oakland, CA); Labov, Simon E. (Berkeley, CA); Benner, W. Henry (Danville, CA)
Observation of duplex DNA-drug noncovalent complexes by electrospray ionization mass spectrometry
We have observed by ESI-MS the noncovalent complex formed between a minor groove binding molecule and a 12 base pair self-complementary oligonucleotide. When the ratio of Distamycin Dm to oligonucleotide was varied, oligonucleotide duplex, 1:1 Dm/oligonucleotide duplex, and 2:1 Dm/oligonucleotide duplex noncovalent complexes were observed, consistent with NMR results for the same sequence and Dm to oligonucleotide duplex concentration ratios. These results indicate that ESI-MS is an effective analytical technique for the detection of specific drug-oligonucleotide duplex noncovalent complexes and that specific noncovalent complexes can be observed reflecting stoichiometry in solution. Additional experiments to determine if ESI-MS can provide information on the specificity and selectivity of additional minor groove binding and intercalating molecules are in progress. 19 refs., 1 fig.
Gale, D.C.; Goodlett, D.R.; Light-Wahl, K.J.; Smith, R.D. (Pacific Northwest Lab., Richland, WA (United States))
PCRElectrospray Ionization Mass Spectrometry The Potential to Change Infectious Disease Diagnostics in
funding and educational honoraria from Abbott Molecular and Ibis Biosciences (D.M.W.). Accepted for publication February 9, 2012. Disclosure: D.M.W. receives research grants, consulting fees, and
Developments and Applications of Electrophoresis and Small Molecule Laser Desorption Ionization Mass Spectrometry
Ultra-sensitive native fluorescence detection of proteins with miniaturized one- and two-dimensional polyacrylamide gel electrophoresis was achieved with laser side-entry excitation, which provides both high excitation power and low background level. The detection limit for R-phycoerythrin protein spots in 1-D SDS-PAGE was as low as 15 fg, which corresponds to 40 thousand molecules only. The average detection limit of six standard native proteins was 5 pg per band and the dynamic range spanned more than 3 orders of magnitude. Approximately 150 protein spots from 30 ng of total Escherichia coli extraction were detected on a 0.8 cm x 1 cm gel in two-dimensional separation. Estrogen-DNA adducts as 4-OHE{sub 1}(E{sub 2})-1-N3Ade and 4-OHEI(E2)-2-NacCys were hypothesized as early risk assessment of prostate and breast cancers. Capillary electrophoresis, luminescence/absorption spectroscopy and LC-MS were used to characterize and detect these adducts. Monoclonal antibodies against each individual adduct were developed and used to enrich such compounds from urine samples of prostate and breast cancer patients as well as healthy people. Adduct 4-OHE{sub 1}-1-N3Ade was detected at much higher level in urine from subjects with prostate cancer patients compared to healthy males. The same adduct and 4-OHEI-2-NacCys were also detected at a much higher level in urine from a woman with breast carcinoma than samples from healthy controls. These two DNA adducts may serve as novel biomarkers for early diagnostic of cancers. The adsorption properties of R-phycoerythrin (RPE), on the fused-silica surface were studied using capillary electrophoresis (CE) and single molecule spectroscopy. The band shapes and migration times were measured in CE. Adsorption and desorption events were recorded at the single-molecule level by imaging of the evanescent-field layer using total internal reflection. The adsorbed RPE molecules on the fused-silica prism surface were counted with confidence based on Imagej software. The capacity factor and desorption rate were estimated from the counting results. The mobility-based adsorption isotherms were constructed from both computer simulations and experiments to determine the capacity factor.
Hui Zhang
High-Resolution Desorption Electrospray Ionization Mass Spectrometry for Chemical Characterization
, University of California-Irvine, Irvine, California 92697 Characterization of the chemical composition solar radiation and modifications of cloud properties.1-6 The extent of radiative forcing and cloud
Novel Analytical Methods for Examining Biomolecular Complexes Using Electrospray Ionization Mass Spectrometry
in solvation energies of the trivalent, ?H solv (3+), anddivalent metal ion, ?H solv (2+), that correspond to theH red ? ? ? H (III) ? ? H solv (3 ? ) ? ? H solv (2 ? ) The
Flick, Tawnya Grace
Dilution-Free Analysis from Picoliter Droplets by Nano-Electrospray Ionization Mass Spectrometry
The expanding role of microfluidics for chemical and biochemical analysis is due to factors including the favorable scaling of separation performance with reduced channel dimensions,[1] flexibility afforded by computer-aided device design, and the ability to integrate multiple sample handling and analysis steps into a single platform.[2] Such devices enable smaller liquid volumes and sample sizes to be handled than can be achieved on the benchtop, where sub-microliter volumes are difficult to work with and where sample losses to the surfaces of multiple reaction vessels become prohibitive. A particularly attractive microfluidic platform for sample-limited analyses employs aqueous droplets or plugs encapsulated by an immiscible oil.[3,4] Each droplet serves as a discrete compartment or reaction chamber enabling, e.g., high throughput screening[5,6] and kinetic studies[7-9] of femto- to nanoliter samples, as well as the encapsulation[10-12] and lysis[10] of individual cells with limited dilution of the cellular contents
Kelly, Ryan T.; Page, Jason S.; Marginean, Ioan; Tang, Keqi; Smith, Richard D.
Detection and quantitation of benzo(a)pyrene-derived DNA adducts in mouse liver by liquid chromatography - tandem mass spectrometry: comparison with P-32-postlabeling
The polycyclic aromatic hydrocarbon, benzo(a)pyrene (B(a)P) is a proven animal carcinogen that is potentially carcinogenic to humans. B( a)P is an ubiquitous environmental pollutant and is also present in tobacco smoke, coal tar, automobile exhaust emissions, and charred food. A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method using electrospray ionization and selected reaction monitoring (SRM) has been developed for the detection of 10-(deoxyguanosin-N{sub 2}-yl)-7,8,9-trihydroxy-7,8,9,10- tetrahydrobenzo(a)pyrene (B(a)PDE-N{sub 2}dG) adducts formed in DNA following the metabolic activation of B(a)P to benzo(a) pyrene-7,8-dihydrodiol-9,10-epoxide (B(a)PDE).
Singh, R.; Gaskell, M.; Le Pla, R.C.; Kaur, B.; Azim-Araghi, A.; Roach, J.; Koukouves, G.; Souliotis, V.L.; Kyrtopoulos, S.A.; Farmer, P.B. [University of Leicester, Leicester (United Kingdom)
RAPID COMMUNICATIONS IN MASS SPECTROMETRY, VOL. 7, 693-699 (1993) Collisions of C&*and Cii at Fluorinated and
energy is relatively high, typically 12-15% for small molecules.' Thus, if the efficiency of energy & Sons, Ltd. (e.g. masses areater than 200u) strike surfaces." The high relative energy transferRAPID COMMUNICATIONS IN MASS SPECTROMETRY, VOL. 7, 693-699 (1993) Collisions of C&*and Cii
1.4.2 Atomic Absorption5.3.2 Atomic Absorption Spectrometry . . . . . . . . . . .ablation and diode laser-atomic absorption spectrometry�,
Optimizing a microwave gas ion source for continuous-flow accelerator mass spectrometry
A 2.45 GHz microwave ion source coupled with a magnesium charge exchange canal (C x C) has been successfully adapted to a large acceptance radiocarbon accelerator mass spectrometry system at the National Ocean Sciences Accelerator Mass Spectrometry (AMS) Facility, Woods Hole Oceanographic Institution. CO{sub 2} samples from various preparation sources are injected into the source through a glass capillary at 370 {mu}l/min. Routine system parameters are about 120-140 {mu}A of negative {sup 12}C current after the C x C, leading to about 400 {sup 14}C counts per second for a modern sample and implying a system efficiency of 0.2%. While these parameters already allow us to perform high-quality AMS analyses on large samples, we are working on ways to improve the output of the ion source regarding emittance and efficiency. Modeling calculations suggest modifications in the extraction triode geometry, shape, and size of the plasma chamber could improve emittance and, hence, ion transport efficiency. Results of experimental tests of these modifications are presented.
Reden, K. F. von; Roberts, M. L.; Burton, J. R.; Beaupre, S. R. [Geology and Geophysics Department, Woods Hole Oceanographic Institution (WHOI), Woods Hole, Massachusetts 02543 (United States)
Standard test method for isotopic abundance analysis of uranium hexa?uoride and uranyl nitrate solutions by multi-collector, inductively coupled plasma-mass spectrometry
Standard test method for isotopic abundance analysis of uranium hexa?uoride and uranyl nitrate solutions by multi-collector, inductively coupled plasma-mass spectrometry
Chemical crosslinking and mass spectrometry studies of the structure and dynamics of membrane proteins and receptors.
Membrane proteins make up a diverse and important subset of proteins for which structural information is limited. In this study, chemical cross-linking and mass spectrometry were used to explore the structure of the G-protein-coupled photoreceptor bovine rhodopsin in the dark-state conformation. All experiments were performed in rod outer segment membranes using amino acid 'handles' in the native protein sequence and thus minimizing perturbations to the native protein structure. Cysteine and lysine residues were covalently cross-linked using commercially available reagents with a range of linker arm lengths. Following chemical digestion of cross-linked protein, cross-linked peptides were identified by accurate mass measurement using liquid chromatography-fourier transform mass spectrometry and an automated data analysis pipeline. Assignments were confirmed and, if necessary, resolved, by tandem MS. The relative reactivity of lysine residues participating in cross-links was evaluated by labeling with NHS-esters. A distinct pattern of cross-link formation within the C-terminal domain, and between loop I and the C-terminal domain, emerged. Theoretical distances based on cross-linking were compared to inter-atomic distances determined from the energy-minimized X-ray crystal structure and Monte Carlo conformational search procedures. In general, the observed cross-links can be explained by re-positioning participating side-chains without significantly altering backbone structure. One exception, between C3 16 and K325, requires backbone motion to bring the reactive atoms into sufficient proximity for cross-linking. Evidence from other studies suggests that residues around K325 for a region of high backbone mobility. These findings show that cross-linking studies can provide insight into the structural dynamics of membrane proteins in their native environment.
Haskins, William E.; Leavell, Michael D.; Lane, Pamela; Jacobsen, Richard B.; Hong, Joohee; Ayson, Marites J.; Wood, Nichole L.; Schoeniger, Joseph S.; Kruppa, Gary Hermann; Sale, Kenneth L.; Young, Malin M.; Novak, Petr
Analysis of fission gas release kinetics by on-line mass spectrometry
The release of fission gas (Xe and Kr) and helium out of nuclear fuel materials in normal operation of a nuclear power reactor can constitute a strong limitation of the fuel lifetime. Moreover, radioactive isotopes of Xe and Kr contribute significantly to the global radiological source term released in the primary coolant circuit in case of accidental situations accompanied by fuel rod loss of integrity. As a consequence, fission gas release investigation is of prime importance for the nuclear fuel cycle economy, and is the driven force of numerous R and D programs. In this domain, for solving current fuel behavior understanding issues, preparing the development of new fuels (e.g. for Gen IV power systems) and for improving the modeling prediction capability, there is a marked need for innovations in the instrumentation field, mainly for: . Quantification of very low fission gas concentrations, released from fuel sample and routed in sweeping lines. Monitoring of quick gas release variations by quantification of elementary release during a short period of time. Detection of a large range of atomic masses (e.g. H{sub 2}, HT, He, CO, CO{sub 2}, Ne, Ar, Kr, Xe), together with a performing separation of isotopes for Xe and Kr elements. Coupling measurement of stable and radioactive gas isotopes, by using in parallel mass spectrometry and gamma spectrometry techniques. To fulfill these challenging needs, a common strategy for analysis equipment implementation has been set up thanks to a recently launched collaboration between the CEA and the Univ. of Provence, with the technological support of the Liverpool Univ.. It aims at developing a chronological series of mass spectrometer devices based upon mass filter and 2D/3D ion traps with Fourier transform operating mode and having increasing levels of performances to match the previous challenges for out-of pile and in-pile experiments. The final objective is to install a high performance online mass spectrometer coupled to a gamma spectrometer in the fission product laboratory of the future Jules Horowitz Material Test Reactor. An intermediate step will consist of testing first equipment on an existing experimental facility in the LECA-STAR Hot Cell Laboratory of the CEA Cadarache. This paper presents the scientific and operational stakes linked to fission gas issues, resumes the current state of art for analyzing them in nuclear facilities, then presents the skills gathered through this collaboration to overcome technological bottlenecks. Finally it describes the implementation strategy in nuclear research facilities of the CEA Cadarache. (authors)
Zerega, Y.; Reynard-Carette, C. [Univ. of Provence, Laboratoire Chimie Provence, UMR 6264, Avenue escadrille Normandie - Niemen, F-13397 Marseille (France); Parrat, D. [CEA, Nuclear Energy Div. DEN, CEA Cadarache, F-13108 Saint-Paul-lez-Durance (France); Carette, M. [Univ. of Provence, Laboratoire Chimie Provence, UMR 6264, Avenue escadrille Normandie - Niemen, F-13397 Marseille (France); Brkic, B. [Univ. of Liverpool, Dept. of Electrical Engineering and Electronics, Liverpool L69 3BX (United Kingdom); Lyoussi, A.; Bignan, G. [CEA, Nuclear Energy Div. DEN, CEA Cadarache, F-13108 Saint-Paul-lez-Durance (France); Janulyte, A.; Andre, J. [Univ. of Provence, Laboratoire Chimie Provence, UMR 6264, Avenue escadrille Normandie - Niemen, F-13397 Marseille (France); Pontillon, Y.; Ducros, G. [CEA, Nuclear Energy Div. DEN, CEA Cadarache, F-13108 Saint-Paul-lez-Durance (France); Taylor, S. [Univ. of Liverpool, Dept. of Electrical Engineering and Electronics, Liverpool L69 3BX (United Kingdom)
A fast microchannel plate-scintillator detector for velocity map imaging and imaging mass spectrometry
The time resolution achievable using standard position-sensitive ion detectors, consisting of a chevron pair of microchannel plates coupled to a phosphor screen, is primarily limited by the emission lifetime of the phosphor, around 70 ns for the most commonly used P47 phosphor. We demonstrate that poly-para-phenylene laser dyes may be employed extremely effectively as scintillators, exhibiting higher brightness and much shorter decay lifetimes than P47. We provide an extensive characterisation of the properties of such scintillators, with a particular emphasis on applications in velocity-map imaging and microscope-mode imaging mass spectrometry. The most promising of the new scintillators exhibits an electron-to-photon conversion efficiency double that of P47, with an emission lifetime an order of magnitude shorter. The new scintillator screens are vacuum stable and show no signs of signal degradation even over longer periods of operation.
Winter, B.; King, S. J.; Vallance, C., E-mail: firstname.lastname@example.com [Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Rd, Oxford OX1 3TA (United Kingdom); Brouard, M., E-mail: email@example.com [Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Rd, Oxford OX1 3QZ (United Kingdom)
Detecting and Removing Data Artifacts in Hadamard Transform Ion Mobility-Mass Spectrometry Measurements
Applying Hadamard transform multiplexing to ion mobility separations (IMS) can significantly improve the signal-to-noise ratio and throughput for IMS coupled mass spectrometry (MS) measurements by increasing the ion utilization efficiency. However, it has been determined that both fluctuations in ion intensity as well as spatial shifts in the multiplexed data lower the signal-to-noise ratios and appear as noise in downstream processing of the data. To address this problem, we have developed a novel algorithm that discovers and eliminates data artifacts. The algorithm uses knowledge of the true signal peaks derived from the encoded data and allows for both artifacts and noise to be removed with high confidence, decreasing the likelihood of false identifications in subsequent data processing. The result is that IMS-MS can be applied to increase measurement sensitivity while avoiding artifacts that have previously limited its utility.
Prost, Spencer A.; Crowell, Kevin L.; Baker, Erin Shammel; Ibrahim, Yehia M.; Clowers, Brian H.; Monroe, Matthew E.; Anderson, Gordon A.; Smith, Richard D.; Payne, Samuel H.
Laser desorption time-of-flight mass spectrometry of ultraviolet photo-processed ices
A new ultra-high vacuum experiment is described that allows studying photo-induced chemical processes in interstellar ice analogues. MATRI{sup 2}CES - a Mass Analytical Tool to study Reactions in Interstellar ICES applies a new concept by combining laser desorption and time-of-flight mass spectrometry with the ultimate goal to characterize in situ and in real time the solid state evolution of organic compounds upon UV photolysis for astronomically relevant ice mixtures and temperatures. The performance of the experimental setup is demonstrated by the kinetic analysis of the different photoproducts of pure methane (CH{sub 4}) ice at 20 K. A quantitative approach provides formation yields of several new species with up to four carbon atoms. Convincing evidence is found for the formation of even larger species. Typical mass resolutions obtained range from M/?M ?320 to ?400 for CH{sub 4} and argon, respectively. Additional tests show that the typical detection limit (in monolayers) is ?0.02 ML, substantially more sensitive than the regular techniques used to investigate chemical processes in interstellar ices.
Paardekooper, D. M., E-mail: email@example.com; Bossa, J.-B.; Isokoski, K.; Linnartz, H., E-mail: email@example.com [Raymond and Beverly Sackler Laboratory for Astrophysics, Leiden Observatory, Leiden University, PO Box 9513, 2300 RA Leiden (Netherlands)
Improved resolution of hydrocarbon structures and constitutional isomers in complex mixtures using Gas Chromatography-Vacuum Ultraviolet-Mass Spectrometry (GC-VUV-MS)
Understanding the composition of complex hydrocarbon mixtures is important for environmental studies in a variety of fields, but many prevalent compounds cannot be confidently identified using traditional gas chromatography-mass spectrometry (GC-MS) techniques. This work uses vacuum-ultraviolet (VUV) ionization to elucidate the structures of a traditionally"unresolved complex mixture" by separating components by GC retention time, tR, and mass-to-charge ratio, m/Q, which are used to determine carbon number, NC, and the number of rings and double bonds, NDBE. Constitutional isomers are resolved based on tR, enabling the most complete quantitative analysis to date of structural isomers in an environmentally-relevant hydrocarbon mixture. Unknown compounds are classified in this work by carbon number, degree of saturation, presence of rings, and degree of branching, providing structural constraints. The capabilities of this analysis are explored using diesel fuel, in which constitutional isomer distribution patterns are shown to be reproducible between carbon numbers and follow predictable rules. Nearly half of the aliphatic hydrocarbon mass is shown to be branched, suggesting branching is more important in diesel fuel than previously shown. The classification of unknown hydrocarbons and the resolution of constitutional isomers significantly improves resolution capabilities for any complex hydrocarbon mixture.
Aerosol Dynamics Inc; Aerodyne Research, Inc.,; Tofwerk AG, Thun; Isaacman, Gabriel; Wilson, Kevin R.; Chan, Arthur W. H.; Worton, David R.; Kimmel, Joel R.; Nah, Theodora; Hohaus, Thorsten; Gonin, Marc; Kroll, Jesse H.; Worsnop, Doug R.; Goldstein, Allen H.
Assessment of Non-traditional Isotopic Ratios by Mass Spectrometry for Analysis of Nuclear Activities: Annual Report Year 2
The objective of this work is to identify isotopic ratios suitable for analysis via mass spectrometry that distinguish between commercial nuclear reactor fuel cycles, fuel cycles for weapons grade plutonium, and products from nuclear weapons explosions. Methods will also be determined to distinguish the above from medical and industrial radionuclide sources. Mass spectrometry systems will be identified that are suitable for field measurement of such isotopes in an expedient manner. Significant progress has been made with this project within the past year: (1) Isotope production from commercial nuclear fuel cycles and nuclear weapons fuel cycles have been modeled with the ORIGEN and MCNPX codes. (2) MCNPX has been utilized to calculate isotopic inventories produced in a short burst fast bare sphere reactor (to approximate the signature of a nuclear weapon). (3) Isotopic ratios have been identified that are good for distinguishing between commercial and military fuel cycles as well as between nuclear weapons and commercial nuclear fuel cycles. (4) Mass spectrometry systems have been assessed for analysis of the fission products of interest. (5) A short-list of forensic ratios have been identified that are well suited for use in portable mass spectrometry systems.
Biegalski, S; Buchholz, B
Application of coincidence ion mass spectrometry for chemical and structural analysis at the sub-micron scale
Surfaces can be probed with a variant of secondary ion mass spectrometry (SIMS) where the bombardment is with a sequence of single keV projectiles, each resolved in time and space, coupled with the separate record of the secondary ions (SIs) ejected...
Balderas, Sara
Atmospheric Amines and Ammonia Measured with a Chemical Ionization Mass Spectrometer (CIMS)
We report ambient measurements of amines and ammonia with a fast response chemical ionization mass spectrometer (CIMS) in a Southeastern U.S. forest in Alabama and a moderately polluted Midwestern site during the summer. In the Alabama forest, mostly C3-amines (from pptv to tens of pptv) and ammonia (up to 2 ppbv) were detected on a daily basis. C3-amines and ammonia showed similar diurnal trends and temperature and wind direction dependences, and were not associated with transported CO and SO2 plumes. Consistent with temperature dependences, amine and ammonia in the gas and aerosol phases showed opposite diurnal trends, indicating gas-to-particle partitioning of amines and ammonia. Temperature dependences also imply reversible processes of amines and ammonia evaporation from soil surfaces in daytime and deposition of amines and ammonia to soil surfaces at nighttime. Various amines (C1-C6) at the pptv level were observed in the transported biomass burning plumes, showing that biomass burning can be a substantial source of amines in the Southeast U.S. At the moderately polluted Kent site, higher concentrations of amines (C1-C6, from pptv to tens of pptv) and ammonia (up to 6 ppbv) were detected. Diurnal variations of C1- to C3-amines and ammonia were correlated with the ambient temperature. C4- to C6-amines showed abrupt increases during the nighttime, suggesting that they were emitted from local sources. These abundant amines and ammonia may in part explain the frequent new particle formation events reported from Kent. Lower amine concentrations at the rural forested site highlight the importance of constraining anthropogenic sources of amines.
You, Y.; Kanawade, V. P.; de Gouw, J. A.; Guenther, Alex B.; Madronich, Sasha; Sierra-Hernandez, M. R.; Lawler, M.; Smith, James N.; Takahama, S.; Ruggeri, G.; Koss, A.; Olson, K.; Baumann, K.; Weber, R. J.; Nenes, A.; Guo, H.; Edgerton, Eric S.; Porcelli, L.; Brune, W. H.; Goldstein, Allen H.; Lee, S.-H
Multivariate analysis of progressive thermal desorption coupled gas chromatography-mass spectrometry.
Thermal decomposition of poly dimethyl siloxane compounds, Sylgard{reg_sign} 184 and 186, were examined using thermal desorption coupled gas chromatography-mass spectrometry (TD/GC-MS) and multivariate analysis. This work describes a method of producing multiway data using a stepped thermal desorption. The technique involves sequentially heating a sample of the material of interest with subsequent analysis in a commercial GC/MS system. The decomposition chromatograms were analyzed using multivariate analysis tools including principal component analysis (PCA), factor rotation employing the varimax criterion, and multivariate curve resolution. The results of the analysis show seven components related to offgassing of various fractions of siloxanes that vary as a function of temperature. Thermal desorption coupled with gas chromatography-mass spectrometry (TD/GC-MS) is a powerful analytical technique for analyzing chemical mixtures. It has great potential in numerous analytic areas including materials analysis, sports medicine, in the detection of designer drugs; and biological research for metabolomics. Data analysis is complicated, far from automated and can result in high false positive or false negative rates. We have demonstrated a step-wise TD/GC-MS technique that removes more volatile compounds from a sample before extracting the less volatile compounds. This creates an additional dimension of separation before the GC column, while simultaneously generating three-way data. Sandia's proven multivariate analysis methods, when applied to these data, have several advantages over current commercial options. It also has demonstrated potential for success in finding and enabling identification of trace compounds. Several challenges remain, however, including understanding the sources of noise in the data, outlier detection, improving the data pretreatment and analysis methods, developing a software tool for ease of use by the chemist, and demonstrating our belief that this multivariate analysis will enable superior differentiation capabilities. In addition, noise and system artifacts challenge the analysis of GC-MS data collected on lower cost equipment, ubiquitous in commercial laboratories. This research has the potential to affect many areas of analytical chemistry including materials analysis, medical testing, and environmental surveillance. It could also provide a method to measure adsorption parameters for chemical interactions on various surfaces by measuring desorption as a function of temperature for mixtures. We have presented results of a novel method for examining offgas products of a common PDMS material. Our method involves utilizing a stepped TD/GC-MS data acquisition scheme that may be almost totally automated, coupled with multivariate analysis schemes. This method of data generation and analysis can be applied to a number of materials aging and thermal degradation studies.
Van Benthem, Mark Hilary; Mowry, Curtis Dale; Kotula, Paul Gabriel; Borek, Theodore Thaddeus, III
Accelerator Mass Spectrometry Measurements of Plutonium in Sediment and Seawater from the Marshall Islands
During the summer 2000, I was given the opportunity to work for about three months as a technical trainee at Lawrence Livermore National Laboratory, or LLNL as I will refer to it hereafter. University of California runs this Department of Energy laboratory, which is located 70 km east of San Francisco, in the small city of Livermore. This master thesis in Radioecology is based on the work I did here. LLNL, as a second U.S.-facility for development of nuclear weapons, was built in Livermore in the beginning of the 1950's (Los Alamos in New Mexico was the other one). It has since then also become a 'science center' for a number of areas like magnetic and laser fusion energy, non-nuclear energy, biomedicine, and environmental science. The Laboratory's mission has changed over the years to meet new national needs. The following two statements were found on the homepage of LLNL (http://www.llnl.gov), at 2001-03-05, where also information about the laboratory and the scientific projects that takes place there, can be found. 'Our primary mission is to ensure that the nation's nuclear weapons remain safe, secure, and reliable and to prevent the spread and use of nuclear weapons worldwide'. 'Our goal is to apply the best science and technology to enhance the security and well-being of the nation and to make the world a safer place.' The Marshall Islands Dose Assessment and Radioecology group at the Health and Ecological Assessments division employed me, and I also worked to some extent with the Centre for Accelerator Mass Spectrometry (CAMS) group. The work I did at LLNL can be divided into two parts. In the first part Plutonium (Pu) measurements in sediments from the Rongelap atoll in Marshall Islands, using Accelerator Mass Spectrometry (AMS) were done. The method for measuring these kinds of samples is well understood at LLNL since soil samples have been measured with AMS for Pu in the past. Therefore it was the results that were of main interest and not the technique. The second part was to take advantage of AMS's very high sensitivity by measure the Pu-concentrations in small volumes (0.04-1 L) of seawater. The technique for using AMS at Pu-measurements in seawater is relatively new and the main task for me was to find out a method that could work in practice. The area where the sediment samples and the water samples were collected are high above background levels for many radionuclides, including Pu, because of the detonation of the nuclear bomb code-named Castle Bravo, in 1954.
Leisvik, M; Hamilton, T
Facilities: NHMFL 14.5 Tesla Fourier Transform Ion Cyclotron Resonance Mass Spectrometer Citation: A Pseudoatomic Model of the COPII Cage Obtained from Cryo-Electron Microscopy and Mass Spectrometry,
Facilities: NHMFL 14.5 Tesla Fourier Transform Ion Cyclotron Resonance Mass Spectrometer Citation ultrahigh-resolution 14.5 tesla Fourier transform ion cyclotron resonance mass spectrometry. The Mag
Accelerated Analyte Uptake on Single Beads in Microliter-scale Batch Separations using Acoustic Streaming: Plutonium Uptake by Anion Exchange for Analysis by Mass Spectrometry
The use of acoustic streaming as a non-contact mixing platform to accelerate mass transport-limited diffusion processes in small volume heterogeneous reactions has been investigated. Single bead anion exchange of plutonium at nanomolar and sub-picomolar concentrations in 20 microliter liquid volumes was used to demonstrate the effect of acoustic mixing. Pu uptake rates on individual ~760 micrometer diameter AG 1x4 anion exchange resin beads were determined using acoustic mixing and compared with Pu uptake rates achieved by static diffusion alone. An 82 MHz surface acoustic wave (SAW) device was placed in contact with the underside of a 384-well microplate containing flat-bottomed semiconical wells. Acoustic energy was coupled into the solution in the well, inducing acoustic streaming. Pu uptake rates were determined by the plutonium remaining in solution after specific elapsed time intervals, using liquid scintillation counting (LSC) for nanomolar concentrations and thermal ionization mass spectrometry (TIMS) analysis for the sub-picomolar concentration experiments. It was found that this small batch uptake reaction could be accelerated by a factor of about five-fold or more, depending on the acoustic power applied.
Paxton, Walter F.; O'Hara, Matthew J.; Peper, Shane M.; Petersen, Steven L.; Grate, Jay W.
Measurement of Ultra-Low Potassium Contaminations with Accelerator Mass Spectrometry
Levels of trace radiopurity in active detector materials is a subject of major concern in low-background experiments. Among the radio-isotopes, $\\k40$ is one of the most abundant and yet whose signatures are difficult to reject. Procedures were devised to measure trace potassium concentrations in the inorganic salt CsI as well as in organic liquid scintillator (LS) with Accelerator Mass Spectrometry (AMS), giving, respectively, the $\\k40$-contamination levels of $\\sim 10^{-10}$ and $\\sim 10^{-13}$ g/g. Measurement flexibilities and sensitivities are improved over conventional methods. The projected limiting sensitivities if no excess of potassium signals had been observed over background are $8 \\times 10^{-13}$ g/g and $3 \\times 10^{-17}$ g/g for the CsI and LS, respectively. Studies of the LS samples indicate that the radioactive contaminations come mainly in the dye solutes, while the base solvents are orders of magnitude cleaner. The work demonstrate the possibilities of measuring naturally-occurring isotopes with the AMS techniques.
K. J. Dong
Levels of trace radiopurity in active detector materials is a subject of major concern in low-background experiments. Among the radio-isotopes, $\\k40$ is one of the most abundant and yet whose signatures are difficult to reject. Procedures were devised to measure trace potassium concentrations in the inorganic salt CsI as well as in organic liquid scintillator (LS) with Accelerator Mass Spectrometry (AMS), giving, respectively, the $\\k40$-contamination levels of $\\sim 10^{-10}$ and $\\sim 10^{-13}$ g/g. Measurement flexibilities and sensitivities are improved over conventional methods. The projected limiting sensitivities if no excess of potassium signals had been observed over background are $8 \\times 10^{-13}$ g/g and $3 \\times 10^{-17}$ g/g for the CsI and LS, respectively. Studies of the LS samples indicate that the radioactive contaminations come mainly in the dye solutes, while the base solvents are orders of magnitude cleaner. The work demonstrate the possibilities of measuring naturally-occurring isoto...
Dong, K J
Determination of the stellar (n,gamma) cross section of 40Ca with accelerator mass spectrometry
The stellar (n,gamma) cross section of 40Ca at kT=25 keV has been measured with a combination of the activation technique and accelerator mass spectrometry (AMS). This combination is required when direct off-line counting of the produced activity is compromised by the long half-life and/or missing gamma-ray transitions. The neutron activations were performed at the Karlsruhe Van de Graaff accelerator using the quasistellar neutron spectrum of kT=25 keV produced by the 7Li(p,n)7Be reaction. The subsequent AMS measurements were carried out at the Vienna Environmental Research Accelerator (VERA) with a 3 MV tandem accelerator. The doubly magic 40Ca is a bottle-neck isotope in incomplete silicon burning, and its neutron capture cross section determines the amount of leakage, thus impacting on the eventual production of iron group elements. Because of its high abundance, 40Ca can also play a secondary role as "neutron poison" for the s-process. Previous determinations of this value at stellar energies were based o...
Dillmann, I; Heil, M; K�ppeler, F; Wallner, A; Forstner, O; Golser, R; Kutschera, W; Priller, A; Steier, P; Mengoni, A; Gallino, R; Paul, M; Vockenhuber, C; 10.1103/PhysRevC.79.065805
The stellar (n,gamma) cross section of 40Ca at kT=25 keV has been measured with a combination of the activation technique and accelerator mass spectrometry (AMS). This combination is required when direct off-line counting of the produced activity is compromised by the long half-life and/or missing gamma-ray transitions. The neutron activations were performed at the Karlsruhe Van de Graaff accelerator using the quasistellar neutron spectrum of kT=25 keV produced by the 7Li(p,n)7Be reaction. The subsequent AMS measurements were carried out at the Vienna Environmental Research Accelerator (VERA) with a 3 MV tandem accelerator. The doubly magic 40Ca is a bottle-neck isotope in incomplete silicon burning, and its neutron capture cross section determines the amount of leakage, thus impacting on the eventual production of iron group elements. Because of its high abundance, 40Ca can also play a secondary role as "neutron poison" for the s-process. Previous determinations of this value at stellar energies were based on time-of-flight measurements. Our method uses an independent approach, and yields for the Maxwellian-averaged cross section at kT=30 keV a value of 30 keV= 5.73+/-0.34 mb.
I. Dillmann; C. Domingo-Pardo; M. Heil; F. K�ppeler; A. Wallner; O. Forstner; R. Golser; W. Kutschera; A. Priller; P. Steier; A. Mengoni; R. Gallino; M. Paul; C. Vockenhuber
Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Analysis of Large Polymerases Chain Reaction Products
We have attempted to expand the size range of PCR products that can be analyzed by electroscopy ionization (ESI) Fourier transformion cyclotron resonance (FTICR) mass spectrometry. The mass measurement accuracy obtained illustrates that a signel base substitution could be identified at the size of PCR product with a 7 tesla ESI-FTICR
Wunschel, David S.(BATTELLE (PACIFIC NW LAB)) [BATTELLE (PACIFIC NW LAB); Pasa Tolic, Ljiljana (BATTELLE (PACIFIC NW LAB)) [BATTELLE (PACIFIC NW LAB); Feng, Bingbing (ASSOC WESTERN UNIVERSITY) [ASSOC WESTERN UNIVERSITY; Smith, Richard D.(BATTELLE (PACIFIC NW LAB)) [BATTELLE (PACIFIC NW LAB)
Hydrothermal Liquefaction Oil and Hydrotreated Product from Pine Feedstock Characterized by Heteronuclear Two-Dimensional NMR Spectroscopy and FT-ICR Mass Spectrometry
Hydrothermal liquefaction (HTL) crude oil and hydrotreated product from pine tree farm waste (forest product residual, FPR) have been analyzed by direct infusion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) in both positive- and negative-ionization modes and high-resolution twodimensional heteronuclear 1H-13C NMR spectroscopy. FT-ICR MS resolves thousands of compounds in complex oils and provides unparalleled compositional details for individual molecules for identification of compound class (heteroatom content), type (number of rings plus double bonds to carbon or double bond equivalents (DBE) and carbon number (degree of alkylation). Heteronuclear 1H-13C NMR spectroscopy provides one-bond and multiple-bond correlations between pairs of 1H and 13C chemical shifts that are characteristic of different organic functional groups. Taken together this information provides a picture of the chemical composition of these oils. Pyrolysis crude oil product from pine wood was characterized for comparison. Generally, pyrolysis oil is comprised of a more diverse distribution of heteroatom classes with higher oxygen number relative to HTL oil as shown by both positive- and negative-ion ESI FT-ICR MS. A total of 300 N1, 594 O1 and 267 O2 compounds were observed as products of hydrotreatment. The relative abundance of N1O1, N1O2, N1O3, N2, N2O1, N2O2 and O3 compounds are reduced to different degrees after hydrotreatment and other higher heteroatom containing species (O4-O10, N1O4, N1O5 and N2O3) are completely removed by hydrotreatment.
Sudasinghe, Nilusha; Cort, John R.; Hallen, Richard T.; Olarte, Mariefel V.; Schmidt, Andrew J.; Schaub, Tanner
A new detector for mass spectrometry: Direct detection of low energy ions using a multi-pixel photon counter
A new type of ion detector for mass spectrometry and general detection of low energy ions is presented. The detector consists of a scintillator optically coupled to a single-photon avalanche photodiode (SPAD) array. A prototype sensor has been constructed from a LYSO (Lu{sub 1.8}Y{sub 0.2}SiO{sub 5}(Ce)) scintillator crystal coupled to a commercial SPAD array detector. As proof of concept, the detector is used to record the time-of-flight mass spectra of butanone and carbon disulphide, and the dependence of detection sensitivity on the ion kinetic energy is characterised.
Wilman, Edward S.; Gardiner, Sara H.; Vallance, Claire [Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Rd, Oxford OX1 3TA (United Kingdom); Nomerotski, Andrei [Department of Physics, University of Oxford, Denys Wilkinson Building, Keble Rd, Oxford OX1 3RH (United Kingdom); Turchetta, Renato [Rutherford Appleton Laboratory, Chilton, Didcot, Oxfordshire OX11 0QX (United Kingdom); Brouard, Mark [Department of Chemistry, University of Oxford, Physical and Theoretical Chemistry Laboratory, South Parks Rd, Oxford OX1 3QZ (United Kingdom)
Measurement of low radioactivity background in a high voltage cable by high resolution inductively coupled plasma mass spectrometry
The measurement of naturally occurring low level radioactivity background in a high voltage (HV) cable by high resolution inductively coupled plasma mass spectrometry (HR ICP MS) is presented in this work. The measurements were performed at the Chemistry Service of the Gran Sasso National Laboratory. The contributions to the radioactive background coming from the different components of the heterogeneous material were separated. Based on the mass fraction of the cable, the whole contamination was calculated. The HR ICP MS results were cross-checked by gamma ray spectroscopy analysis that was performed at the low background facility STELLA (Sub Terranean Low Level Assay) of the LNGS underground lab using HPGe detectors.
Vacri, M. L. di; Nisi, S.; Balata, M. [Gran Sasso National Laboratory, Chemistry Service, SS 17bis km 18.910, 67100 Assergi (Aq) (Italy)] [Gran Sasso National Laboratory, Chemistry Service, SS 17bis km 18.910, 67100 Assergi (Aq) (Italy)
Mass spectrometry imaging (MSI) enables researchers to directly probe endogenous molecules directly within the architecture of the biological matrix. Unfortunately, efficient access, management, and analysis of the data generated by MSI approaches remain major challenges to this rapidly developing field. Despite the availability of numerous dedicated file formats and software packages, it is a widely held viewpoint that the biggest challenge is simply opening, sharing, and analyzing a file without loss of information. Here we present OpenMSI, a software framework and platform that addresses these challenges via an advanced, high-performance, extensible file format and Web API for remote data access (http://openmsi.nersc.gov). The OpenMSI file format supports storage of raw MSI data, metadata, and derived analyses in a single, self-describing format based on HDF5 and is supported by a large range of analysis software (e.g., Matlab and R) and programming languages (e.g., C++, Fortran, and Python). Careful optimization of the storage layout of MSI data sets using chunking, compression, and data replication accelerates common, selective data access operations while minimizing data storage requirements and are critical enablers of rapid data I/O. The OpenMSI file format has shown to provide >2000-fold improvement for image access operations, enabling spectrum and image retrieval in less than 0.3 s across the Internet even for 50 GB MSI data sets. To make remote high-performance compute resources accessible for analysis and to facilitate data sharing and collaboration, we describe an easy-to-use yet powerful Web API, enabling fast and convenient access to MSI data, metadata, and derived analysis results stored remotely to facilitate high-performance data analysis and enable implementation of Web based data sharing, visualization, and analysis.
Rubel, Oliver; Greiner, Annette; Cholia, Shreyas; Louie, Katherine; Bethel, E. Wes; Northen, Trent R.; Bowen, Benjamin P.
Copyright0 1988by San FranciscoPress,Inc., BOX6800, San Franc&o, CA 94101&fM, USA Laser Microprobe Mass Spectrometry
Copyright0 1988by San FranciscoPress,Inc., BOX6800, San Franc&o, CA 94101&fM, USA 10 Laser. Bennett, W. Lauwers, A. Vertes, and R. Gijbels Laser microprobe mass spectrometry (LMMS)em- ploys
Vertes, Akos
Probing Molecular Associations of Field-Collected and Laboratory-Generated SOA with Nano-DESI High-Resolution Mass Spectrometry
Aerosol samples from the 2010 CalNex field study in Bakersfield (BF) and Los Angeles (LA) were analyzed using positive mode nanospray-desorption electrospray ionization mass spectrometry (nano-DESI-MS). Secondary organic aerosol (SOA) produced in a photochemical chamber by photooxidation of diesel (DSL) fuel and isoprene (ISO) under humid, high-NOx conditions, was analyzed for comparison. Three groups of organic compounds with zero, one, or two nitrogen atoms in their molecular formulas (0N, 1N, 2N) were compared in detail. The composition of ambient SOA exhibited greater overlap with DSL than with ISO. The overlap of the chamber experiments with the BF data was relatively consistent throughout the day while the overlap with LA data increased significantly in the noon-6pm sample, consistent with the SOA plume arriving from downtown Los Angeles. BF samples were more oxidized, contained more organic nitrogen, and had more overlap with the chamber data compared to LA samples. The addition of gaseous ammonia (NH3) to the DSL experiment was necessary to generate many of the 2N compounds observed in BF. This analysis demonstrates that DSL and ISO were important sources but cannot account for all of the observed ambient compounds indicating that other sources of organics were also likely important.
O'Brien, Rachel E.; Nguyen, Tran B.; Laskin, Alexander; Laskin, Julia; Hayes, Patrick L.; Liu, Shang; Jimenez, Jose L.; Russell, Lynn M.; Nizkorodov, Sergey; Goldstein, Allen H.
{sup 99}Tc bioassay by inductively coupled plasma mass spectrometry (ICP-MS)
A means of analyzing {sup 99}Tc in urine by inductively coupled plasma mass spectrometry (ICP-MS) has been developed. Historically, {sup 99}Tc analysis was based on the radiometric detection of the 293 keV E{sub Max} beta decay product by liquid scintillation or gas flow proportional counting. In a urine matrix, the analysis of{sup 99}Tc is plagued with many difficulties using conventional radiometric methods. Difficulties originate during chemical separation due to the volatile nature of Tc{sub 2}O{sub 7} or during radiation detection due to color or chemical quenching. A separation scheme for {sup 99}Tc detection by ICP-MS is given and is proven to be a sensitive and robust analytical alternative. A comparison of methods using radiometric and mass quantitation of {sup 99}Tc has been conducted in water, artificial urine, and real urine matrices at activity levels between 700 and 2,200 dpm/L. Liquid scintillation results based on an external standard quench correction and a quench curve correction method are compared to results obtained by ICP-MS. Each method produced accurate results, however the precision of the ICP-MS results is superior to that of liquid scintillation results. Limits of detection (LOD) for ICP-MS and liquid scintillation detection are 14.67 and 203.4 dpm/L, respectively, in a real urine matrix. In order to determine the basis for the increased precision of the ICP-MS results, the detection sensitivity for each method is derived and measured. The detection sensitivity for the {sup 99}Tc isotope by ICP-MS is 2.175 x 10{sup {minus}7} {+-} 8.990 x 10{sup {minus}9} and by liquid scintillation is 7.434 x 10{sup {minus}14} {+-} 7.461 x 10{sup {minus}15}. A difference by seven orders of magnitude between the two detection systems allows ICP-MS samples to be analyzed for a period of 15 s compared to 3,600 s by liquid scintillation counting with a lower LOD.
Lewis, L.A.
Analysis of liquified coal for nitrogenous bases; separation by high performance liquid chromatography and identification by probe microdistillation/mass spectrometry
ANALYSIS OF LIQUIFIED COAL FOR NITROGENOUS BASES; SEPARATION BY HIGH PERFORMANCE LIQUID CHROMATOGRAPHY AND IDENTIFICATION BY PROBE MICRODISTILLATION/MASS SPECTROMETRY A Thesis by LEONARD ROYCE SCHRONK Submitted to the Graduate College... AND IDENTIFICATION BY PROBE MICRODISTILLATION/MASS SPECTROMETRY A Thesis by LEONARD ROYCE SCHRONK Approved as to style and content by: Co-Charrman o Commlxtte ) (Co-Chazrman o Committee Me er Hea of Department December 1978 ABSTRACT Analysis of Liquified...
Schronk, Leonard Royce
Development of A Cryogenic Drift Cell Spectrometer and Methods for Improving the Analytical Figures of Merit for Ion Mobility-Mass Spectrometry Analysis
A cryogenic (325-80 K) ion mobility-mass spectrometer was designed and constructed in order to improve the analytical figures-of-merit for the chemical analysis of small mass analytes using ion mobility-mass spectrometry. The instrument incorporates...
May, Jody C.
A new method for the determination of {sup 237}Np and Pu isotopes in large soil samples has been developed that provides enhanced uranium removal to facilitate assay by inductively coupled plasma mass spectrometry (ICP-MS). This method allows rapid preconcentration and separation of plutonium and neptunium in large soil samples for the measurement of {sup 237}Np and Pu isotopes by ICP-MS. {sup 238}U can interfere with {sup 239}Pu measurement by ICP-MS as {sup 238}UH{sup +} mass overlap and {sup 237}Np via {sup 238}U peak tailing. The method provides enhanced removal of uranium by separating Pu and Np initially on TEVA Resin, then transferring Pu to DGA resin for additional purification. The decontamination factor for removal of uranium from plutonium for this method is greater than 1 x 10{sup 6}. Alpha spectrometry can also be applied so that the shorter-lived {sup 238}Pu isotope can be measured successfully. {sup 239}Pu, {sup 242}Pu and {sup 237}Np were measured by ICP-MS, while {sup 236}Pu and {sup 238}Pu were measured by alpha spectrometry.
Maxwell, S.
High resolution mass spectrometry method and system for analysis of whole proteins and other large molecules
A matrix assisted laser desorption/ionization (MALDI) method and related system for analyzing high molecular weight analytes includes the steps of providing at least one matrix-containing particle inside an ion trap, wherein at least one high molecular weight analyte molecule is provided within the matrix-containing particle, and MALDI on the high molecular weight particle while within the ion trap. A laser power used for ionization is sufficient to completely vaporize the particle and form at least one high molecular weight analyte ion, but is low enough to avoid fragmenting the high molecular weight analyte ion. The high molecular weight analyte ion is extracted out from the ion trap, and is then analyzed using a detector. The detector is preferably a pyrolyzing and ionizing detector.
Reilly, Peter T. A. (Knoxville, TN) [Knoxville, TN; Harris, William A. (Naperville, IL) [Naperville, IL
Measurement of Trace I-129 Concentrations in CsI Powder and Organic Liquid Scintillator with Accelerator Mass Spectrometry
Levels of trace radiopurity in active detector materials is a subject of major concern in low-background experiments. Procedures were devised to measure trace concentrations of I-129 in the inorganic salt CsI as well as in organic liquid scintillator with Accelerator Mass Spectrometry (AMS) which leads to improvement in sensitivities by several orders of magnitude over other methods. No evidence of their existence in these materials were observed. Limits of scintillator, respectively, were derived.These are the first results in a research program whose goals are to develop techniques to measure trace radioactivity in detector materials by AMS.
Measurement of Trace $^{129}I$ Concentrations in CsI Powder and Organic Liquid Scintillator with Accelerator Mass Spectrometry
affinity-purification mass spectrometry: Topics by E-print Network
give comments on precautions Proposed Structure: Nominal Mass (low res.) Accurate Mass (high res.) Atomic Composition*) MSMS (CID) Resolution Polarity: Positive Negative *) Atomic...
International Journal of Mass Spectrometry 248 (2006) 18 Molecular hydrogen ion elimination from alkyl iodides
reported on many occasions [17]. Recently, we have studied the ionization/dissociation pro- cesses of some 26510 98695. E-mail address: email@example.com (C. Kosmidis). ethane, propane, etc.) has been studied of propane, Tonokura et al. [13] have shown that the atomic hydrogen elim- ination channel exhibits a site
Strathclyde, University of
International Journal of Mass Spectrometry and Ion Processes, 94 (1989) 63-85 Elsevier Science Publishers B.V., Amsterdam -Printed in The Netherlands
in the understanding of the formation of mass spectra, among them the unexpectedly high kinetic energy of the laserInternational Journal of Mass Spectrometry and Ion Processes, 94 (1989) 63-85 Elsevier Science, cloud extensions, ion yields, relative sensitivity factors and ion kinetic energy distributions, i
Studies of the mechanism of the cluster formation in a thermally sampling atmospheric pressure ionization mass spectrometer
In this study a thermally sampling atmospheric pressure ionization mass spectrometer is described and characterized. The ion transfer stage offers the capability to sample cluster ions at thermal equilibrium and during this transfer fundamental processes possibly affecting the cluster distribution are also readily identified. Additionally, the transfer stage combines optional collision-induced dissociation (CID) analysis of the cluster composition with thermal equilibrium sampling of clusters. The performance of the setup is demonstrated with regard to the proton-bound water cluster system. The benefit of the studied processes is that they can help to improve future transfer stages and to understand cluster ion reactions in ion mobility tubes and high-pressure ion sources. In addition, the instrument allows for the identification of fragmentation and protonation reactions caused by CID.
Albrecht, Sascha, E-mail: email@example.com; Stroh, Fred, E-mail: firstname.lastname@example.com [Forschungszentrum J�lich GmbH, Institute of Energy and Climate Research, Stratosphere (IEK-7), 52428 J�lich (Germany)] [Forschungszentrum J�lich GmbH, Institute of Energy and Climate Research, Stratosphere (IEK-7), 52428 J�lich (Germany); Klopotowski, Sebastian, E-mail: email@example.com; Derpmann, Valerie, E-mail: firstname.lastname@example.com; Klee, Sonja, E-mail: email@example.com; Brockmann, Klaus J., E-mail: firstname.lastname@example.com; Benter, Thorsten, E-mail: firstname.lastname@example.com [Physical and Theoretical Chemistry, Institute for Pure and Applied Mass Spectrometry, University of Wuppertal, 42097 Wuppertal (Germany)] [Physical and Theoretical Chemistry, Institute for Pure and Applied Mass Spectrometry, University of Wuppertal, 42097 Wuppertal (Germany)
Validating mass spectrometry measurements of nuclear materials via a non-contact volume analysis method of ion sputter craters
A combination of secondary ion mass spectrometry, optical profilometry and a statistically-driven algorithm was used to develop a non-contact volume analysis method to validate the useful yields of nuclear materials. The volume analysis methodology was applied to ion sputter craters created in silicon and uranium substrates sputtered by 18.5 keV O- and 6.0 keV Ar+ ions. Sputter yield measurements were determined from the volume calculations and were shown to be comparable to Monte Carlo calculations and previously reported experimental observations. Additionally, the volume calculations were used to determine the useful yields of Si+, SiO+ and SiO2+ ions from the silicon substrate and U+, UO+ and UO2+ ions from the uranium substrate under 18.5 keV O- and 6.0 keV Ar+ ion bombardment. This work represents the first steps toward validating the interlaboratory and cross-platform performance of mass spectrometry for the analysis of nuclear materials.
Willingham, David G.; Naes, Benjamin E.; Fahey, Albert J.
Enhancement of concentration range of chromatographically detectable components with array detector mass spectrometry
Methods and instruments for high dynamic range analysis of sample components are described. A sample is subjected to time-dependent separation, ionized, and the ions dispersed with a constant integration time across an array of detectors according to the ions m/z values. Each of the detectors in the array has a dynamically adjustable gain or a logarithmic response function, producing an instrument capable of detecting a ratio of responses or 4 or more orders of magnitude.
Enke, Christie
chamber is made of stainless steel tube, with most of the surface area (80%) replaced with a 0.01-inch diameter tungsten wire grid. Another tungsten wire (electron ionization filament) is wrapped around the electrode with ~ 5 mm distance from... sparking between the high voltage components and the insulators, which ultimately leads to unstable performance of the ion source. The thermal electron emission tungsten filament deteriorates with usage as well. Signs of an aged filament include: high...
High Precision Atomic Mass Spectrometry with Applications to Neutrino Physics, Fundamental Constants and Physical Chemistry.
?? The Florida State University single-ion cryogenic Penning trap mass spectrometer has been used to precisely measure the masses of the doublets 76Ge/76Se and 74Ge/74Se� (more)
Mount, Brianna Jane
Efficient mass-selective three-photon ionization of zirconium atoms
In an AVLIS process, .sup.91 Zr is selectively removed from natural zirconium by a three-step photoionization wherein Zr atoms are irradiated by a laser beam having a wavelength .lambda..sub.1, selectively raising .sup.91 Zr atoms to an odd-parity E.sub.1 energy level in the range of 16000-19000 cm.sup.-1, are irradiated by a laser beam having a wavelength .lambda..sub.2 to raise the atoms from an E.sub.l level to an even-parity E.sub.2 energy level in the range of 35000-37000 cm.sup.-1 and are irradiated by a laser beam having a wavelength .lambda..sub.3 to cause a resonant transition of atoms from an E.sub.2 level to an autoionizing level above 53506 cm.sup.-1. .lambda..sub.3 wavelengths of 5607, 6511 or 5756 .ANG. will excite a zirconium atom from an E.sub.2 energy state of 36344 cm.sup.-1 to an autoionizing level; a .lambda..sub.3 wavelength of 5666 .ANG. will cause an autoionizing transition from an E.sub.2 level of 36068 cm.sup.-1 ; and a .lambda. .sub.3 wavelength of 5662 .ANG. will cause an ionizing resonance of an atom at an E.sub.2 level of 35904 cm.sup.-1.
Page, Ralph H. (San Ramon, CA)
Ion fragmentation in an electrospray ionization mass spectrometer interface with different gases
in the gas phase. However, particularly in multi- component samples, this may not be enough to unambigu predicts that the degree of ion fragmentation increases with increasing mass of the curtain gas. However with argon and krypton is caused by condensation of the gases within the free jet expansion between
Chen, David D.Y.
Rapid Quantitation of Ascorbic and Folic Acids in SRM 3280 Multivitamin/Multielement Tablets using Flow-Injection Tandem Mass Spectrometry
RATIONALE: Ascorbic acid (AA) and folic acid (FA) are water-soluble vitamins and are usually fortified in food and dietary supplements. For the safety of human health, proper intake of these vitamins is recommended. Improvement in the analysis time required for the quantitative determination of these vitamins in food and nutritional formulations is desired. METHODS: A simple and fast (~5 min) in-tube sample preparation was performed, independently for FA and AA, by mixing extraction solvent with a powdered sample aliquot followed by agitation, centrifugation, and filtration to recover an extract for analysis. Quantitative detection was achieved by flow-injection (1 L injection volume) electrospray ionization tandem mass spectrometry (ESI-MS/MS) in negative ion mode using the method of standard addition. RESULTS: Method of standard addition was employed for the quantitative estimation of each vitamin in a sample extract. At least 2 spiked and 1 non-spiked sample extract were injected in triplicate for each quantitative analysis. Given an injection-to-injection interval of approximately 2 min, about 18 min was required to complete the quantitative estimation of each vitamin. The concentration values obtained for the respective vitamins in the standard reference material (SRM) 3280 using this approach were within the statistical range of the certified values provided in the NIST Certificate of Analysis. The estimated limit of detections of FA and AA were 13 and 5.9 ng/g, respectively. CONCLUSIONS: Flow-injection ESI-MS/MS was successfully applied for the rapid quantitation of FA and AA in SRM 3280 multivitamin/multielement tablets.
Bhandari, Deepak [ORNL] [ORNL; Kertesz, Vilmos [ORNL] [ORNL; Van Berkel, Gary J [ORNL] [ORNL
Molecular Resolution and Fragmentation of Fulvic Acid by Electrospray Ionization/Multistage Tandem
investigated by electrospray ionization/ion trap multistage tandem mass spectrometry (ESI/MST/ MS). ESI% water mobile phase found that negative ion detection gave the optimum generation of parent ions that can and specific high molecular weight standards found multiply charged negative ions that gave a low bias
Deconstruction of Activity-Dependent Covalent Modification of Heme in Human Neutrophil Myeloperoxidase by Multistage Mass Spectrometry (MS[superscript 4])
Myeloperoxidase (MPO) is known to be inactivated and covalently modified by treatment with hydrogen peroxide and agents similar to 3-(2-ethoxypropyl)-2-thioxo-2,3-dihydro-1H-purin-6(9H)-one (1), a 254.08 Da derivative of 2-thioxanthine. Peptide mapping by liquid chromatography and mass spectrometry detected modification by 1 in a labile peptide-heme-peptide fragment of the enzyme, accompanied by a mass increase of 252.08 Da. The loss of two hydrogen atoms was consistent with mechanism-based oxidative coupling. Multistage mass spectrometry (MS{sup 4}) of the modified fragment in an ion trap/Orbitrap spectrometer demonstrated that 1 was coupled directly to heme. Use of a 10 amu window delivered the full isotopic envelope of each precursor ion to collision-induced dissociation, preserving definitive isotopic profiles for iron-containing fragments through successive steps of multistage mass spectrometry. Iron isotope signatures and accurate mass measurements supported the structural assignments. Crystallographic analysis confirmed linkage between the methyl substituent of the heme pyrrole D ring and the sulfur atom of 1. The final orientation of 1 perpendicular to the plane of the heme ring suggested a mechanism consisting of two consecutive one-electron oxidations of 1 by MPO. Multistage mass spectrometry using stage-specific collision energies permits stepwise deconstruction of modifications of heme enzymes containing covalent links between the heme group and the polypeptide chain.
Geoghegan, Kieran F.; Varghese, Alison H.; Feng, Xidong; Bessire, Andrew J.; Conboy, James J.; Ruggeri, Roger B.; Ahn, Kay; Spath, Samantha N.; Filippov, Sergey V.; Conrad, Steven J.; Carpino, Philip A.; Guimar�es, Cristiano R.W.; Vajdos, Felix F. (Pfizer)
Development and Application of an Electrospray Ionization Ion Mobility-mass Spectrometer Using an RF Ion Funnel and Periodic-focusing Ion Guide
home-built electrospray ionization (ESI) source and rf ion funnel(IF) as an ion transfer interface, modular periodic-focusing ion guide (PFIG) as a drift tube (DT) for arrival time measurement, and orthogonally accelerated linear time-of-flight mass...
Jeon, Junho
A World without Sample Preparation: Developing Rapid Uranium Isotope Measurement Capabilities by Resonance Ionization Mass Spectrometry (RIMS)
We are developing highly sensitive, highly discriminating laser-based techniques for rapid determination of isotopic compositions. Rapid command of such information is critical to assessment of the origin and history of nuclear materials, particularly in post-detonation scenarios.
Knight, K B; Hutcheon, I D; Isselhardt, B H; Savina, M R; Prussin, S G
A Dual Platform for Selective Analyte Enrichment and Ionization in Mass Spectrometry Using Aptamer-Conjugated Graphene Oxide
-Conjugated Graphene Oxide Basri Gulbakan, Emir Yasun, M. Ibrahim Shukoor, Zhi Zhu, Mingxu You, Xiaohong Tan,, Hernan: This study demonstrates the use of aptamer-conju- gated graphene oxide as an affinity extraction a matrix and with greatly improved signal- to-noise ratios. Aptamer-conjugated graphene oxide has clear
Tan, Weihong
Distance Restraints from Crosslinking Mass Spectrometry: Mining a Molecular Dynamics Simulation Database to Evaluate Lysine-Lysine Distances
Integrative structural biology models the structures of protein complexes that are intractable by classical structural methods (because of extreme size, dynamics, or heterogeneity) by combining computational structural modeling with data from experimental methods. One such method is chemical cross-linking mass spectrometry (XL-MS), in which cross-linked peptides, derived from a covalently cross-linked protein complex and identified by liquid chromatography-mass spectrometry, pinpoint protein residues close in three-dimensional space. The commonly used lysine-reactive N-hydroxysuccinimide ester reagents disuccinimidylsuberate (DSS) and bis(sulfosuccinimidyl)suberate (BS3) have a linker arm that is 11.4 � long when fully extended. However, XL-MS studies on proteins of known structure frequently report cross-links that exceed this distance. Typically, a tolerance of ~3 � is added to the theoretical maximum to account for this observation, with little justification for the value chosen. We used the Dynameomics database, a repository of high-quality molecular dynamics simulations of 807 proteins representative of all protein folds, to investigate the change in lysine-lysine distances resulting from native-state dynamics on the time-scale of tens of nanoseconds. We conclude that observed cross-links are consistent with a protein structure if the distance between cross-linked lysine N? atoms is less than the cross-linker length plus 11.3 �. For DSS or BS3, this corresponds to a C? to C? distance of 30.4 �. This analysis provides a theoretical basis for the widespread practice of adding a tolerance to the crosslinker length when comparing XL-MS results to structures, and indicates the appropriate values of an XLMS derived distance constraint to use in structural modeling.
Merkley, Eric D.; Rysavy, Steven; Kahraman, Abdullah; Hafen, Ryan P.; Daggett, Valerie; Adkins, Joshua N.
Principal ComponentAnalysisof Optical EmissionSpectroscopy and MassSpectrometry:Applicationto Reactive Ion Etch
of process parameters (i.e., pressure, RF power, and gas mixture) on the optical emission and mass spectra.g., chamber pressure, RF power, and gas flow, while others are internal to the condition of the chamber, e
Shadmehr, Reza
Organic aerosol components observed in Northern Hemispheric datasets from Aerosol Mass Spectrometry
In this study we compile and present results from the factor analysis of 43 Aerosol Mass Spectrometer (AMS) datasets (27 of the datasets are reanalyzed in this work). The components from all sites, when taken together, ...
Kroll, Jesse
Qualitative and quantitative analysis of proteolytically digested glycoproteins by mass spectrometry
of glycoproteins, and it is particularly useful in the detection of glycosylation present on proteins. Most glycoproteins are prepared for mass spectrometric analysis by performing a protease digestion, followed by either a separation by HPLC or some other...
Rebecchi, Kathryn
Determination of particulate lead using aerosol mass spectrometry: MILAGRO/MCMA-2006 observations
We report the first measurements of particulate lead (Pb) from Aerodyne Aerosol Mass Spectrometers, which were deployed in and around Mexico City during the Megacity Initiative: Local and Global Research Observations ...
Salcedo, D.
New Mass and Lifetime Measurements of $^{152}$Sm Projectile Fragments with Time-Resolved Schottky Mass Spectrometry
The FRS-ESR facilities at GSI provide unique conditions for precision measurements with stored exotic nuclei over a large range in the chart of nuclides. In the present experiment the exotic nuclei were produced via fragmentation of $^{152}$Sm projectiles in a thick beryllium target at 500-600 MeV/u, separated in-flight with the fragment separator FRS, and injected into the storage-cooler ring ESR. Mass and lifetime measurements have been performed with bare and few-electron ions. The experiment and first results will be presented in this contribution.
Yu. A. Litvinov; F. Bosch; H. Geissel; H. Weick; K. Beckert; P. Beller; D. Boutin; C. Brandau; L. Chen; O. Klepper; R. Kn�bel; C. Kozhuharov; J. Kurcewicz; S. A. Litvinov; M. Mazzocco; G. M�nzenberg; C. Nociforo; F. Nolden; W. Pla�; C. Scheidenberger; M. Steck; B. Sun; M. Winkler
International Journal of Mass Spectrometry and Zon Processes, 78 (1987) 357-392 Elsevier Science Publishers B.V., Amsterdam -Printed in The Netherlands
that significant radial energy transport determines the yields for water ice sputtering at high excitationInternational Journal of Mass Spectrometry and Zon Processes, 78 (1987) 357-392 Elsevier Science, an effective area, and an effective depth, which is determined by the radial dissipation of energy when ions
Johnson, Robert E.
International Journal of Mass Spectrometry and Ion Processes, 78 (1987) 237-250 Elsevier Science Publishers B.V., Amsterdam -Printed in The Netherlands
of interest with high energy (- 100 MeV) 252Cf fission fragments [l]. This high-energy desorptionInternational Journal of Mass Spectrometry and Ion Processes, 78 (1987) 237-250 Elsevier Science polypeptide. Details of the slow unimolecular decay of high molecular weight multiply protonated polypeptides
Interface for the rapid analysis of liquid samples by accelerator mass spectrometry
An interface for the analysis of liquid sample having carbon content by an accelerator mass spectrometer including a wire, defects on the wire, a system for moving the wire, a droplet maker for producing droplets of the liquid sample and placing the droplets of the liquid sample on the wire in the defects, a system that converts the carbon content of the droplets of the liquid sample to carbon dioxide gas in a helium stream, and a gas-accepting ion source connected to the accelerator mass spectrometer that receives the carbon dioxide gas of the sample in a helium stream and introduces the carbon dioxide gas of the sample into the accelerator mass spectrometer.
Turteltaub, Kenneth; Ognibene, Ted; Thomas, Avi; Daley, Paul F; Salazar Quintero, Gary A; Bench, Graham
Aerosol Mass Spectrometry via Laser-Induced Incandescence Particle Vaporization Final Report
We have successfully developed and commercialized a soot particle aerosol mass spectrometer (SP-AMS) instrument to measure mass, size, and chemical information of soot particles in ambient environments. The SP-AMS instrument has been calibrated and extensively tested in the laboratory and during initial field studies. The first instrument paper describing the SP-AMS has been submitted for publication in a peer reviewed journal and there are several related papers covering initial field studies and laboratory studies that are in preparation. We have currently sold 5 SP-AMS instruments (either as complete systems or as SP modules to existing AMS instrument operators).
Timothy B. Onasch
Precise ruthenium fission product isotopic analysis using dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS)
99Tc is a subsurface contaminant of interest at numerous federal, industrial, and international facilities. However, as a mono-isotopic fission product, 99Tc lacks the ability to be used as a signature to differentiate between the different waste disposal pathways that could have contributed to subsurface contamination at these facilities. Ruthenium fission-product isotopes are attractive analogues for the characterization of 99Tc sources because of their direct similarity to technetium with regard to subsurface mobility, and their large fission yields and low natural background concentrations. We developed an inductively coupled plasma mass spectrometry (ICP-MS) method capable of measuring ruthenium isotopes in groundwater samples and extracts of vadose zone sediments. Samples were analyzed directly on a Perkin Elmer ELAN DRC II ICP-MS after a single pass through a 1-ml bed volume of Dowex AG 50W-X8 100-200 mesh cation exchange resin. Precise ruthenium isotopic ratio measurements were achieved using a low-flow Meinhard-type nebulizer and long sample acquisition times (150,000 ms). Relative standard deviations of triplicate replicates were maintained at less than 0.5% when the total ruthenium solution concentration was 0.1 ng/ml or higher. Further work was performed to minimize the impact caused by mass interferences using the dynamic reaction cell (DRC) with O2 as the reaction gas. The aqueous concentrations of 96Mo and 96Zr were reduced by more than 99.7% in the reaction cell prior to injection of the sample into the mass analyzer quadrupole. The DRC was used in combination with stable-mass correction to quantitatively analyze samples containing up to 2-orders of magnitude more zirconium and molybdenum than ruthenium. The analytical approach documented herein provides an efficient and cost-effective way to precisely measure ruthenium isotopes and quantitate total ruthenium (natural vs. fission-product) in aqueous matrixes.
Brown, Christopher F.; Dresel, P. Evan; Geiszler, Keith N.; Farmer, Orville T.
Analyzing Nuclear Fuel Cycles from Isotopic Ratios of Waste Products Applicable to Measurement by Accelerator Mass Spectrometry
An extensive study was conducted to determine isotopic ratios of nuclides in spent fuel that may be utilized to reveal historical characteristics of a nuclear reactor cycle. This forensic information is important to determine the origin of unknown nuclear waste. The distribution of isotopes in waste products provides information about a nuclear fuel cycle, even when the isotopes of uranium and plutonium are removed through chemical processing. Several different reactor cycles of the PWR, BWR, CANDU, and LMFBR were simulated for this work with the ORIGEN-ARP and ORIGEN 2.2 codes. The spent fuel nuclide concentrations of these reactors were analyzed to find the most informative isotopic ratios indicative of irradiation cycle length and reactor design. Special focus was given to long-lived and stable fission products that would be present many years after their creation. For such nuclides, mass spectrometry analysis methods often have better detection limits than classic gamma-ray spectroscopy. The isotopic ratios {sup 151}Sm/{sup 146}Sm, {sup 149}Sm/{sup 146}Sm, and {sup 244}Cm/{sup 246}Cm were found to be good indicators of fuel cycle length and are well suited for analysis by accelerator mass spectroscopy.
Biegalski, S R; Whitney, S M; Buchholz, B
Multiphoton ionization of large water clusters
Water clusters are multimers of water molecules held together by hydrogen bonds. In the present work, multiphoton ionization in the UV range coupled with time of flight mass spectrometry has been applied to water clusters with up to 160 molecules in order to obtain information on the electronic states of clusters of different sizes up to dimensions that can approximate the bulk phase. The dependence of ion intensities of water clusters and their metastable fragments produced by laser ionization at 355 nm on laser power density indicates a (3+1)-photon resonance-enhanced multiphoton ionization process. It also explains the large increase of ionization efficiency at 355 nm compared to that at 266 nm. Indeed, it was found, by applying both nanosecond and picosecond laser ionization with the two different UV wavelengths, that no water cluster sequences after n = 9 could be observed at 266 nm, whereas water clusters up to m/z 2000 Th in reflectron mode and m/z 3000 Th in linear mode were detected at 355 nm. The agreement between our findings on clusters of water, especially true in the range with n > 10, and reported data for liquid water supports the hypothesis that clusters above a critical dimension can approximate the liquid phase. It should thus be possible to study clusters just above 10 water molecules, for getting information on the bulk phase structure.
Apicella, B., E-mail: firstname.lastname@example.com [Combustion Research Institute, IRC�C.N.R., P.le Tecchio 80, 80125 Napoli (Italy); Li, X. [Key Laboratory of Power Machinery and Engineering, Ministry of Education, Shanghai Jiao Tong University, Shanghai 200240 (China); Passaro, M. [CNISM and Chemical Engineering, Materials and Industrial Production Department, University of Naples �Federico II,� P.le Tecchio 80, 80125 Napoli (Italy); Spinelli, N. [CNISM and Physics Department, University of Naples �Federico II,� Via Cintia, 80124 Napoli (Italy); Wang, X. [SPIN�C.N.R., Via Cintia, 80124 Napoli (Italy)
Determination of thorium in seawater by neutron activation analysis and mass spectrometry
The recent development of neutron activation analysis and mass spectrometric methods for the determination of /sup 232/Th in seawater has made possible rapid sampling and analysis of this long-lived, non-radiogenic thorium isotope on small-volume samples. The marine geochemical utility of /sup 232/Th, whose concentration in seawater is extremely low, warrants the development of these sensitive techniques. The analytical methods and some results are presented and discussed in this article. 24 refs., 3 figs.
Huh, Chih-An
Mass Spectrometry Analysis of Proteome-wide Proteolytic Post-translational
AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE:1 First Use of Energy for All Purposes (Fuel and Nonfuel),Feet) Year Jan Feb Mar Apr MayAtmospheric Optical Depth7-1D: VegetationEquipment Surfaces andMapping the Nanoscale Landscape PrintSurveyMary K.Mass
Standard test method for determination of impurities in nuclear grade uranium compounds by inductively coupled plasma mass spectrometry
1.1 This test method covers the determination of 67 elements in uranium dioxide samples and nuclear grade uranium compounds and solutions without matrix separation by inductively coupled plasma mass spectrometry (ICP-MS). The elements are listed in Table 1. These elements can also be determined in uranyl nitrate hexahydrate (UNH), uranium hexafluoride (UF6), triuranium octoxide (U3O8) and uranium trioxide (UO3) if these compounds are treated and converted to the same uranium concentration solution. 1.2 The elements boron, sodium, silicon, phosphorus, potassium, calcium and iron can be determined using different techniques. The analyst's instrumentation will determine which procedure is chosen for the analysis. 1.3 The test method for technetium-99 is given in Annex A1. 1.4 The values stated in SI units are to be regarded as standard. 1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish ...
The effect of ultrafast laser wavelength on ablation properties and implications on sample introduction in inductively coupled plasma mass spectrometry
We investigated the role of femtosecond (fs) laser wavelength on laser ablation (LA) and its relation to laser generated aerosol counts and particle distribution, inductively coupled plasma-mass spectrometry (ICP-MS) signal intensity, detection limits, and elemental fractionation. Four different NIST standard reference materials (610, 613, 615, and 616) were ablated using 400 nm and 800 nm fs laser pulses to study the effect of wavelength on laser ablation rate, accuracy, precision, and fractionation. Our results show that the detection limits are lower for 400 nm laser excitation than 800 nm laser excitation at lower laser energies but approximately equal at higher energies. Ablation threshold was also found to be lower for 400 nm than 800 nm laser excitation. Particle size distributions are very similar for 400 nm and 800 nm wavelengths; however, they differ significantly in counts at similar laser fluence levels. This study concludes that 400 nm LA is more beneficial for sample introduction in ICP-MS, particularly when lower laser energies are to be used for ablation.
LaHaye, N. L.; Harilal, S. S.; Diwakar, P. K.; Hassanein, A. [Center for Materials under Extreme Environment, School of Nuclear Engineering Purdue University, West Lafayette, Indiana 47907 (United States); Kulkarni, P. [Centers for Disease Control and Prevention, National Institute of Occupational Safety and Health, Cincinnati, Ohio 45213 (United States)
Determination of secondary ion mass spectrometry relative sensitivity factors for polar and non-polar ZnO
Zinc oxide (ZnO) is regarded as a promising material for optoelectronic devices, due to its electronic properties. Solely, the difficulty in obtaining p-type ZnO impedes further progress. In this connection, the identification and quantification of impurities is a major demand. For quantitative information using secondary ion mass spectrometry (SIMS), so-called relative sensitivity factors (RSF) are mandatory. Such conversion factors did not yet exist for ZnO. In this work, we present the determined RSF values for ZnO using primary (ion implanted) as well as secondary (bulk doped) standards. These RSFs have been applied to commercially available ZnO substrates of different surface termination (a-plane, Zn-face, and O-face) to quantify the contained impurities. Although these ZnO substrates originate from the same single-crystal, we observe discrepancies in the impurity concentrations. These results cannot be attributed to surface termination dependent RSF values for ZnO.
Laufer, Andreas; Volbers, Niklas; Eisermann, Sebastian; Meyer, Bruno K. [Physikalisches Institut, Justus-Liebig-Universitaet Giessen, Heinrich-Buff-Ring 16, 35392 Giessen (Germany); Potzger, Kay [Helmholtz-Zentrum Dresden-Rossendorf, Bautzner Landstrasse 400, 01328 Dresden (Germany); Geburt, Sebastian; Ronning, Carsten [Institut fuer Festkoerperphysik, Universitaet Jena, Max-Wien-Platz 1, 07743 Jena (Germany)
Characterization of a Sealed Americium-Beryllium (AmBe) Source by Inductively Coupled Plasma Mass Spectrometry
Two Americium-Beryllium neutron sources were dismantled, sampled (sub-sampled) and analyzed via inductively coupled plasma mass spectrometry (ICP-MS). Characteristics such as �age� since purification, actinide content, trace metal content and inter and intra source composition were determined. The �age� since purification of the two sources was determined to be 25.0 and 25.4 years, respectively. The systematic errors in the �age� determination were � 4 % 2s. The amount and isotopic composition of U and Pu varied substantially between the sub-samples of Source 2 (n=8). This may be due to the physical means of sub-sampling or the way the source was manufactured. Source 1 was much more consistent in terms of content and isotopic composition (n=3 sub-samples). The Be-Am ratio varied greatly between the two sources. Source 1 had an Am-Be ratio of 6.3 � 52 % (1s). Source 2 had an Am-Be ratio of 9.81 � 3.5 % (1s). In addition, the trace element content between the samples varied greatly. Significant differences were determined between Source 1 and 2 for Sc, Sr, Y, Zr, Mo, Ba and W.
James Sommers; Marcos Jimenez; Mary Adamic; Jeffrey Giglio; Kevin Carney
Recommendations for mass spectrometry data quality metrics for open access data(corollary to the Amsterdam principles)
Policies supporting the rapid and open sharing of proteomic data are being implemented by the leading journals in the field. The proteomics community is taking steps to ensure that data are made publicly accessible and are of high quality, a challenging task that requires the development and deployment of methods for measuring and documenting data quality metrics. On September 18, 2010, the U.S. National Cancer Institute (NCI) convened the 'International Workshop on Proteomic Data Quality Metrics' in Sydney, Australia, to identify and address issues facing the development and use of such methods for open access proteomics data. The stakeholders at the workshop enumerated the key principles underlying a framework for data quality assessment in mass spectrometry data that will meet the needs of the search community, journals, funding agencies, and data repositories. Attendees discussed and agreed upon two primary needs for the wide use of quality metrics: (i)an evolving list of comprehensive quality metrics and (ii)standards accompanied by software analytics. Attendees stressed the importance of increased education and training programs to promote reliable protocols in proteomics. This workshop report explores the historic precedents, key discussions, and necessary next steps to enhance the quality of open access data. By agreement, this article is published simultaneously in Proteomics, Proteomics Clinical Applications, Journal of Proteome Research, and Molecular and Cellular Proteomics, as a public service to the research community.The peer review process was a coordinated effort conducted by a panel of referees selected by the journals.
Kingsinger, Christopher R.; Apffel, James; Baker, Mark S.; Bian, Xiaopeng; Borchers, Christoph H.; Bradshaw, Ralph A.; Brusniak, Mi-Youn; Chan, Daniel W.; Deutsch, Eric W.; Domon, Bruno; Gorman, Jeff; Grimm, Rudolf; Hancock, William S.; Hermjakob, Henning; Horn, David; Hunter, Christie; Kolar, Patrik; Kraus, Hans-Joachim; Langen, Hanno; Linding, Rune; Moritz, Robert L.; Omenn, Gilbert S.; Orlando, Ron; Pandey, Akhilesh; Ping, Peipei; Rahbar, Amir; Rivers, Robert; Seymour, Sean L.; Simpson, Richard J.; Slotta, Douglas; Smith, Richard D.; Stein, Stephen E.; Tabb, David L.; Tagle, Danilo; Yates, John R.; Rodriguez, Henry
Enrichment and Analysis of Nonenzymatically Glycated Peptides: Boronate Affinity Chromatography Coupled with Electron-Transfer Dissociation Mass Spectrometry
Non-enzymatic glycation of peptides and proteins by D-glucose has important implications in the pathogenesis of diabetes mellitus, particularly in the development of diabetic complications. However, no effective high-throughput methods exist for identifying proteins containing this low abundance post-translational modification in bottom-up proteomic studies. In this report, phenylboronate affinity chromatography was used in a two-step enrichment scheme to selectively isolate first glycated proteins and then glycated, tryptic peptides from human serum glycated in vitro. Enriched peptides were subsequently analyzed by alternating electron transfer dissociation (ETD) and collision induced dissociation (CID) tandem mass spectrometry. It was observed that ETD fragmentation mode resulted in a significantly higher number of glycated peptide identifications (87.6% of all identified peptides) versus CID mode (17.0% of all identified peptides), when utilizing dual glycation enrichment on both the protein and peptide level. This study illustrates that phenylboronate affinity chromatography coupled with LC-MS/MS with ETD as the fragmentation mode is an efficient approach for analyses of glycated proteins and can have broad applications in studies of diabetes mellitus.
Zhang, Qibin; Tang, Ning; Brock, Jonathan W.; Mottaz, Heather M.; Ames, Jennifer M.; Baynes, John; Smith, Richard D.; Metz, Thomas O.
Radial arrays of nano-electrospray ionization emitters and methods of forming electrosprays
Electrospray ionization emitter arrays, as well as methods for forming electrosprays, are described. The arrays are characterized by a radial configuration of three or more nano-electrospray ionization emitters without an extractor electrode. The methods are characterized by distributing fluid flow of the liquid sample among three or more nano-electrospray ionization emitters, forming an electrospray at outlets of the emitters without utilizing an extractor electrode, and directing the electrosprays into an entrance to a mass spectrometry device. Each of the nano-electrospray ionization emitters can have a discrete channel for fluid flow. The nano-electrospray ionization emitters are circularly arranged such that each is shielded substantially equally from an electrospray-inducing electric field.
Kelly, Ryan T [West Richland, WA; Tang, Keqi [Richland, WA; Smith, Richard D [Richland, WA
Fundamental studies of the plasma extraction and ion beam formation processes in inductively coupled plasma mass spectrometry
The fundamental and practical aspects are described for extracting ions from atmospheric pressure plasma sources into an analytical mass spectrometer. Methodologies and basic concepts of inductively coupled plasma mass spectrometry (ICP-MS) are emphasized in the discussion, including ion source, sampling interface, supersonic expansion, slumming process, ion optics and beam focusing, and vacuum considerations. Some new developments and innovative designs are introduced. The plasma extraction process in ICP-MS was investigated by Langmuir measurements in the region between the skimmer and first ion lens. Electron temperature (T{sub e}) is in the range 2000--11000 K and changes with probe position inside an aerosol gas flow. Electron density (n{sub e}) is in the range 10{sup 8}--10{sup 10} {sup {minus}cm }at the skimmer tip and drops abruptly to 10{sup 6}--10{sup 8} cm{sup {minus}3} near the skimmer tip and drops abruptly to 10{sup 6}--10{sup 8} cm{sup {minus}3} downstream further behind the skimmer. Electron density in the beam leaving the skimmer also depends on water loading and on the presence and mass of matrix elements. Axially resolved distributions of electron number-density and electron temperature were obtained to characterize the ion beam at a variety of plasma operating conditions. The electron density dropped by a factor of 101 along the centerline between the sampler and skimmer cones in the first stage and continued to drop by factors of 10{sup 4}--10{sup 5} downstream of skimmer to the entrance of ion lens. The electron density in the beam expansion behind sampler cone exhibited a 1/z{sup 2} intensity fall-off (z is the axial position). An second beam expansion originated from the skimmer entrance, and the beam flow underwent with another 1/z{sup 2} fall-off behind the skimmer. Skimmer interactions play an important role in plasma extraction in the ICP-MS instrument.
Niu, Hongsen
Homeland security relies heavily on analytical chemistry to identify suspicious materials and persons. Traditionally this role has focused on attribution, determining the type and origin of an explosive, for example. But as technology advances, analytical chemistry can and will play an important role in the prevention and preemption of terrorist attacks. More sensitive and selective detection techniques can allow suspicious materials and persons to be identified even before a final destructive product is made. The work presented herein focuses on the use of commercial and novel detection techniques for application to the prevention of terrorist activities. Although drugs are not commonly thought of when discussing terrorism, narcoterrorism has become a significant threat in the 21st century. The role of the drug trade in the funding of terrorist groups is prevalent; thus, reducing the trafficking of illegal drugs can play a role in the prevention of terrorism by cutting off much needed funding. To do so, sensitive, specific, and robust analytical equipment is needed to quickly identify a suspected drug sample no matter what matrix it is in. Single Particle Aerosol Mass Spectrometry (SPAMS) is a novel technique that has previously been applied to biological and chemical detection. The current work applies SPAMS to drug analysis, identifying the active ingredients in single component, multi-component, and multi-tablet drug samples in a relatively non-destructive manner. In order to do so, a sampling apparatus was created to allow particle generation from drug tablets with on-line introduction to the SPAMS instrument. Rules trees were developed to automate the identification of drug samples on a single particle basis. A novel analytical scheme was also developed to identify suspect individuals based on chemical signatures in human breath. Human breath was sampled using an RTube{trademark} and the trace volatile organic compounds (VOCs) were preconcentrated using solid phase microextraction (SPME) and identified using gas chromatography - mass spectrometry (GC-MS). Modifications to the sampling apparatus allowed for increased VOC collection efficiency, and reduced the time of sampling and analysis by over 25%. The VOCs are present in breath due to either endogenous production, or exposure to an external source through absorption, inhalation, or ingestion. Detection of these exogenous chemicals can provide information on the prior location and activities of the subject. Breath samples collected before and after exposure in a hardware store and nail salon were analyzed to investigate the prior location of a subject; breath samples collected before and after oral exposure to terpenes and terpenoid compounds, pseudoephedrine, and inhalation exposure to hexamine and other explosive related compounds were analyzed to investigate the prior activity of a subject. The elimination of such compounds from the body was also monitored. In application, this technique may provide an early warning system to identify persons of interest in the prevention and preemption stages of homeland security.
Martin, A N
Spatially resolved chemical imaging of individual atmospheric particles using nanoscale imaging mass spectrometry: Insighs into particle origin and chemistry
Knowledge of the spatially-resolved composition of atmospheric particles is essential for differentiating between their surface versus bulk chemistry, understanding particle reactivity and the potential environmental impact. We demonstrate the application of nanometer-scale secondary ion mass spectrometry (Cameca NanoSIMS 50 ion probe) for 3D chemical imaging of individual atmospheric particles without any sample pre-treatment, such as the sectioning of particles. Use of NanoSIMS depth profile analysis enables elemental mapping of particles with nanometer spatial resolution over a broad of range of particle sizes. We have used this technique to probe spatially resolved composition of ambient particles collected during a field campaign in Mexico City. Particles collected during this campaign have been extensively characterized in the past using other particle analysis techniques and hence offer a unique opportunity for exploring the utility of depth resolved chemical imaging in ambient particle research. 1 Particles examined in this study include those collected during a pollution episode related to urban waste incineration as well as background particles from the same location prior to the episode. Particles from the pollution episode show substantial intra-particle compositional variability typical of particles resulting from multiple emission sources. In contrast, the background particles have relatively homogeneous compositions with enhanced presence of nitrogen, oxygen and chlorine at the particle surface. The observed surface enhancement of nitrogen and oxygen species is consistent with the presence of surface nitrates resulting from gas-particle heterogeneous interactions and is indicative of atmospheric ageing of the particles. The results presented here illustrate 3D characterization of ambient particles for insights into their chemical history.
Ghosal, Sutapa; Weber, Peter K.; Laskin, Alexander
Periostin, discovered by nano-flow liquid chromatography and mass spectrometry, is a novel marker of diabetic retinopathy
Research highlights: {yields} In proliferative membrane and epiretinal membrane specimens, the numbers of proteins are 225 and 154, respectively, and 123 proteins are common to both. {yields} Periostin and thrombospondin-1 proteins are unique to the proliferative membrane specimens. {yields} The expression of periostin is significantly up-regulated in proliferative membrane specimens. -- Abstract: Diabetes can lead to serious microvascular complications including proliferative diabetic retinopathy (PDR), the leading cause of blindness in adults. Recent studies using gene array technology have attempted to apply a hypothesis-generating approach to elucidate the pathogenesis of PDR, but these studies rely on mRNA differences, which may or may not be related to significant biological processes. To better understand the basic mechanisms of PDR and to identify potential new biomarkers, we performed shotgun liquid chromatography (LC)/tandem mass spectrometry (MS/MS) analysis on pooled protein extracts from neovascular membranes obtained from PDR specimens and compared the results with those from non-vascular epiretinal membrane (ERM) specimens. We detected 226 distinct proteins in neovascular membranes and 154 in ERM. Among these proteins, 102 were specific to neovascular membranes and 30 were specific to ERM. We identified a candidate marker, periostin, as well as several known PDR markers such as pigment epithelium-derived factor (PEDF). We then performed RT-PCR using these markers. The expression of periostin was significantly up-regulated in proliferative membrane specimens. Periostin induces cell attachment and spreading and plays a role in cell adhesion. Proteomic analysis by LC/MS/MS, which permits accurate quantitative comparison, was useful in identifying new candidates such as periostin potentially involved in the pathogenesis of PDR.
Takada, Michiya [Division of Diabetes, Metabolism and Endocrinology, Department of Internal Medicine, Showa University School of Medicine, Tokyo (Japan)] [Division of Diabetes, Metabolism and Endocrinology, Department of Internal Medicine, Showa University School of Medicine, Tokyo (Japan); Ban, Yoshiyuki, E-mail: firstname.lastname@example.com [Division of Diabetes, Metabolism and Endocrinology, Department of Internal Medicine, Showa University School of Medicine, Tokyo (Japan)] [Division of Diabetes, Metabolism and Endocrinology, Department of Internal Medicine, Showa University School of Medicine, Tokyo (Japan); Yamamoto, Gou [Department of Oral Pathology and Diagnosis, School of Dentistry, Showa University, Tokyo (Japan)] [Department of Oral Pathology and Diagnosis, School of Dentistry, Showa University, Tokyo (Japan); Ueda, Toshihiko; Saito, Yuta; Nishimura, Eiichi; Fujisawa, Kunimi; Koide, Ryohei [Department of Ophthalmology, Showa University School of Medicine, Tokyo (Japan)] [Department of Ophthalmology, Showa University School of Medicine, Tokyo (Japan); Mizutani, Masakazu; Kozawa, Tadahiko; Shiraishi, Yuji [Kozawa Eye Hospital and Diabetes Center, Ibaraki-ken (Japan)] [Kozawa Eye Hospital and Diabetes Center, Ibaraki-ken (Japan); Bando, Yasuhiko [Biosys Technologies, Inc., Meguro, Tokyo (Japan)] [Biosys Technologies, Inc., Meguro, Tokyo (Japan); Tachikawa, Tetsuhiko [Department of Oral Pathology and Diagnosis, School of Dentistry, Showa University, Tokyo (Japan)] [Department of Oral Pathology and Diagnosis, School of Dentistry, Showa University, Tokyo (Japan); Hirano, Tsutomu [Division of Diabetes, Metabolism and Endocrinology, Department of Internal Medicine, Showa University School of Medicine, Tokyo (Japan)] [Division of Diabetes, Metabolism and Endocrinology, Department of Internal Medicine, Showa University School of Medicine, Tokyo (Japan)
Salt Tolerance of Desorption Electrospray Ionization (DESI)
Suppression of ion intensity in the presence of high salt matrices is common in most mass spectrometry ionization techniques. Desorption electrospray ionization (DESI) is an ionization method that exhibits salt tolerance, and this is investigated. DESI analysis was performed on three different drug mixtures in the presence of 0, 0.2, 2, 5, 10, and 20% NaCl:KCl weight by volume from seven different surfaces. At physiological concentrations individual drugs in each mixture were observed with each surface. Collision-induced dissociation (CID) was used to provide additional confirmation for select compounds. Multiple stage experiments, to MS5, were performed for select compounds. Even in the absence of added salt, the benzodiazepine containing mixture yielded sodium and potassium adducts of carbamazepine which masked the ions of interest. These adducts were eliminated by adding 0.1% 7M ammonium acetate to the standard methanol:water (1:1) spray solvent. Comparison of the salt tolerance of DESI with that of electrospray ionization (ESI) demonstrated much better signal/noise characteristics for DESI in this study. The salt tolerance of DESI was also studied by performing limit of detection and dynamic range experiments. Even at a salt concentration significantly above physiological concentrations, select surfaces were effective in providing spectra that allowed the ready identification of the compounds of interest. The already high salt tolerance of DESI can be optimized further by appropriate choices of surface and spray solution.
Jackson, Ayanna U. [Purdue University; Talaty, Nari [Purdue University; Cooks, R G [Purdue University; Van Berkel, Gary J [ORNL
at the cell surface are upregulated within a few hours of purine removal from the media, while other key purine salvage components are upregulated later in the time-course...
BIOLOGICAL ANALYSIS Mass Spectrometry
Microscope) Analytical Equipment � High Performance Liquid Chromatography � Fast Protein Liquid Chromatography � Gas Chromatography � GC/MS � Elemental Analyser Molecular Biology Equipment � Biorad PCR Machine reactor for scale up studies In-line Particle sizers Rheometers Separation tanks Oscillating column (4m
Greenaway, Alan
EMSL - Mass Spectrometry
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Characterization of human expired breath by solid phase microextraction and analysis using gas chromatography-mass spectrometry and differential mobility spectrometry
Breath analysis has potential to become a new medical diagnostic modality. In this thesis, a method for the analysis of human expired breath was developed using gas chromatography-mass spectroscopy. It was subsequently ...
Merrick, William (William F. W.)
E-Print Network 3.0 - absorption spectrometry etaas Sample Search...
With Confirmation of Accuracy by Inductively Coupled Plasma Mass Spectrometry and Atomic Absorption Spectrometry... -LEAFS uses absorption; graphite furnace; inductively...
Towards secondary ion mass spectrometry on the helium ion microscope: An experimental and simulation based feasibility study with He{sup +} and Ne{sup +} bombardment
The combination of the high-brightness He{sup +}/Ne{sup +} atomic level ion source with secondary ion mass spectrometry detection capabilities opens up the prospect of obtaining chemical information with high lateral resolution and high sensitivity on the Zeiss ORION helium ion microscope. The analytical performance in terms of sputtering yield, useful yield, and detection limit is studied and subsequently optimized by oxygen and cesium flooding. Detection limits down to 10{sup -6} and 10{sup -5} can be obtained for silicon using Ne{sup +} and He{sup +}, respectively. A simulation based study reveals furthermore that a lateral resolution <10 nm can be obtained.
Wirtz, T.; Vanhove, N.; Pillatsch, L.; Dowsett, D. [Department of Science and Analysis of Materials (SAM), Centre de Recherche Public - Gabriel Lippmann, 41 rue du Brill, L-4422 Belvaux (Luxembourg); Sijbrandij, S.; Notte, J. [Carl Zeiss NTS LLC, One Corporation Way, Peabody, Massachusetts 01960 (United States)
A Perspective on the Maillard Reaction and the Analysis of Protein Glycation by Mass Spectrometry: Probing the Pathogenesis of Chronic Disease
The Maillard reaction, starting from the glycation of protein and progressing to the formation of advanced glycation end-products (AGEs), is implicated in the development of complications of diabetes mellitus, as well as in the pathogenesis of cardiovascular, renal, and neurodegenerative diseases. In this perspective review, we provide on overview on the relevance of the Maillard reaction in the pathogenesis of chronic disease and discuss traditional approaches and recent developments in the analysis of glycated proteins by mass spectrometry. We propose that proteomics approaches, particularly bottom-up proteomics, will play a significant role in analyses of clinical samples leading to the identification of new markers of disease development and progression.
Zhang, Qibin; Ames, Jennifer M.; Smith, Richard D.; Baynes, John; Metz, Thomas O.
High Sensitivity Combined with Extended Structural Coverage of Labile Compounds via Nanoelectrospray Ionization at Subambient Pressures
Subambient pressure ionization with nanoelectrospray (SPIN) has proven to be effective in producing ions with high efficiency and transmitting them to low pressures for high sensitivity mass spectrometry (MS) analysis. Here we present evidence that not only does the SPIN source improve MS sensitivity but also allows for gentler ionization conditions. The gentleness of a conventional heated capillary electrospray ionization (ESI) source and the SPIN source was compared by the liquid chromatography mass spectrometry (LC-MS) analysis of colominic acid. Colominic acid is a mixture of sialic acid polymers of different lengths containing labile glycosidic linkages between monomer units necessitating a gentle ion source. By coupling the SPIN source with high resolution mass spectrometry and using advanced data processing tools, we demonstrate much extended coverage of sialic acid polymer chains as compared to using the conventional ESI source. Additionally we show that SPIN-LC-MS is effective in elucidating polymer features with high efficiency and high sensitivity previously unattainable by the conventional ESI-LC-MS methods. ?
Cox, Jonathan T.; Kronewitter, Scott R.; Shukla, Anil K.; Moore, Ronald J.; Smith, Richard D.; Tang, Keqi
Metabolic Differences in Microbial Cell Populations Revealed by Nanophotonic Ionization
ellular differences are linked to cell differentiation, the proliferation of cancer and to the development of drug resistance in microbial infections. Due to sensitivity limitations, however, large- scale metabolic analysis at the single cell level is only available for cells significantly larger in volume than Saccharomyces cerevisiae (~30 fL). Here we demonstrate that by a nanophotonic ionization platform and mass spectrometry, over one hundred up to 108 metabolites, or up to 18% of the known S. cerevisiae metabolome, can be identified in very small cell populations (n < 100). Under ideal conditions, r Relative quantitation of up to 4% of the metabolites is achieved at the single cell level.
Walker, Bennett [George Washington University] [George Washington University; Antonakos, Cory [George Washington University] [George Washington University; Retterer, Scott T [ORNL] [ORNL; Vertes, Akos [George Washington University] [George Washington University
Depth distribution of lithium in oxidized binary Al-Li alloys determined by secondary ion mass spectrometry and neutron depth profiling
Oxidation of binary Al-Li alloys during short exposures at 530 C and long exposures at 200 C was studied with regard to the Li distribution. Secondary ion mass spectrometry (SIMS) and neutron depth profiling (NDP) were used to obtain quantitative Li depth profiles across the surface oxide layer and the underlying alloy. The underlying alloy was depleted in Li as a result of oxidation at 530 and 200 C. The SIMS and NDP results showed good mutual agreement and were used to evaluate the oxide thickness, the Li concentration at the oxide-ally interface, and the mass balance between oxide and alloy. The Li depletion profiles in the alloy were also calculated using the interdiffusion coefficients reported in the literature and compared with the measured profiles; the two profiles differed at 530 C but showed good agreement at 200 C.
Soni, K.K. (Univ. of Chicago, IL (United States)); Williams, D.B. (Lehigh Univ., Bethlehem, PA (United States)); Newbury, D.E.; Chi, P.; Downing, R.G.; Lamaza, G. (National Inst. of Standards and Technology, Gaithersburg, MD (United States))
Comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry of coal liquids produced during a coal liquefaction process
Comprehensive two-dimensional gas chromatography (GC) coupled to time-of-flight mass spectrometry (MS) has been applied to the analysis of coal-derived liquids from the former British Coal Point-of-Ayr coal liquefaction plant. The feed to the hydrocracker and the resulting product were analyzed. The results refer almost exclusively to the plant-derived recycle solvent, known as the liquefaction solvent; the molecular mass range of the GC does not exceed that of the solvent. The method allows for the resolution of the numerous structural isomers of tetralin and methyl indan, one pair of hydrogen-donor (necessary for the dissolution of coal) and isomeric nondonor (that reduce the hydrogen donors) components of the recycle solvent. In addition, the n-alkanes that concentrate in the recycle solvent are easily observed in comparison with the results from one-dimensional GC-MS. 24 refs., 6 figs., 1 tab.
Jacqui F. Hamilton; Alistair. C. Lewis; Marcos Millan; Keith D. Bartle; Alan A. Herod; Rafael Kandiyoti [University of York, York (United Kingdom). Department of Chemistry
A Search for Low-Mass Weakly Interacting Massive Particles Using Voltage-Assisted Calorimetric Ionization Detection in the SuperCDMS Experiment
SuperCDMS is an experiment designed to directly detect weakly interacting massive particles (WIMPs), a favored candidate for dark matter ubiquitous in the Universe. In this Letter, we present WIMP-search results using a calorimetric technique we call CDMSlite, which relies on voltage-assisted Luke-Neganov amplification of the ionization energy deposited by particle interactions. The data were collected with a single 0.6 kg germanium detector running for ten live days at the Soudan Underground Laboratory. A low energy threshold of (electron equivalent) was obtained, which allows us to constrain new WIMP-nucleon spin-independent parameter space for WIMP masses below 6 GeV/c^2.
Agnese, R.; Anderson, A. J.; Asai, M.; Balakishiyeva, D.; Basu Thakur, R.; Bauer, D. A.; Billard, J.; Borgland, A.; Bowles, M. A.; Brandt, D.; Brink, P. L.; Bunker, R.; Cabrera, B.; Caldwell, D. O.; Cerdeno, D. G.; Chagani, H.; Cooley, J.; Cornell, B.; Crewdson, C. H.; Cushman, Priscilla B.; Daal, M.; Di Stefano, P. C.; Doughty, T.; Esteban, L.; Fallows, S.; Figueroa-Feliciano, E.; Godfrey, G. L.; Golwala, S. R.; Hall, Jeter C.; Harris, H. R.; Hertel, S. A.; Hofer, T.; Holmgren, D.; Hsu, L.; Huber, M. E.; Jastram, A.; Kamaev, O.; Kara, B.; Kelsey, M. H.; Kennedy, A.; Kiveni, M.; Koch, K.; Loer, B.; Lopez Asamar, E.; Mahapatra, R.; Mandic, V.; Martinez, C.; McCarthy, K. A.; Mirabolfathi, N.; Moffatt, R. A.; Moore, D. C.; Nadeau, P.; Nelson, R. H.; Page, K.; Partridge, R.; Pepin, M.; Phipps, A.; Prasad, K.; Pyle, M.; Qiu, H.; Rau, W.; Redi, P.; Reisetter, A.; Ricci, Y.; Saab, T.; Sadoulet, B.; Sander, J.; Schneck, K.; Schnee, Richard; Scorza, S.; Serfass, B.; Shank, B.; Speller, D.; Villano, A. N.; Welliver, B.; Wright, D. H.; Yellin, S.; Yen, J. J.; Young, B. A.; Zhang, J.
High-resolution time-of-flight mass spectrometry fingerprinting of metabolites from cecum and distal colon contents of rats fed resistant starch
Time-of-flight mass spectrometry along with statistical analysis was utilized to study metabolic profiles among rats fed resistant starch (RS) diets. Fischer 344 rats were fed four starch diets consisting of 55 % (w/w, dbs) starch. A control starch diet consisting of corn starch was compared against three RS diets. The RS diets were high-amylose corn starch (HA7), HA7 chemically modified with octenyl succinic anhydride, and stearic-acid-complexed HA7 starch. A subgroup received antibiotic treatment to determine if perturbations in the gut microbiome were long lasting. A second subgroup was treated with azoxymethane (AOM), a carcinogen. At the end of the 8-week study, cecal and distal colon content samples were collected from the sacrificed rats. Metabolites were extracted from cecal and distal colon samples into acetonitrile. The extracts were then analyzed on an accurate-mass time-of-flight mass spectrometer to obtain their metabolic profile. The data were analyzed using partial least-squares discriminant analysis (PLS-DA). The PLS-DA analysis utilized a training set and verification set to classify samples within diet and treatment groups. PLS-DA could reliably differentiate the diet treatments for both cecal and distal colon samples. The PLS-DA analyses of the antibiotic and no antibiotic-treated subgroups were well classified for cecal samples and modestly separated for distal colon samples. PLS-DA analysis had limited success separating distal colon samples for rats given AOM from those not treated; the cecal samples from AOM had very poor classification. Mass spectrometry profiling coupled with PLS-DA can readily classify metabolite differences among rats given RS diets.
Anderson, Timothy J. [Ames Laboratory; Jones, Roger W. [Ames Laboratory; Ai, Yongfeng [Iowa State University; Houk, Robert S. [Ames Laboratory; Jane, Jay-lin [Iowa State University; Zhao, Yinsheng [Iowa State University; Birt, Diane F. [Iowa State University; McClelland, John F. [Ames Laboratory
Ionization Thresholds of Small Carbon Clusters: Tunable VUVExperiments and Theory
Small carbon clusters (Cn, n = 2-15) are produced in amolecular beam by pulsed laser vaporization and studied with vacuumultraviolet (VUV) photoionization mass spectrometry. The required VUVradiation in the 8-12 eV range is provided by the Advanced Light Source(ALS) at the Lawrence Berkeley National Laboratory. Mass spectra atvarious ionization energies reveal the qualitative relative abundances ofthe neutral carbon clusters produced. By far the most abundant species isC3. Using the tunability of the ALS, ionization threshold spectra arerecorded for the clusters up to 15 atoms in size. The ionizationthresholds are compared to those measured previously with charge-transferbracketing methods. To interpret the ionization thresholds for differentcluster sizes, new ab initio calculations are carried out on the clustersfor n = 4-10. Geometric structures are optimized at the CCSD(T) levelwith cc-pVTZ (or cc-pVDZ) basis sets, and focal point extrapolations areapplied to both neutral and cation species to determine adiabatic andvertical ionization potentials. The comparison of computed and measuredionization potentials makes it possible to investigate the isomericstructures of the neutral clusters produced in this experiment. Themeasurements are inconclusive for the n = 4-6 species because ofunquenched excited electronic states. However, the data provide evidencefor the prominence of linear structures for the n = 7, 9, 11, 13 speciesand the presence of cyclic C10.
Belau, Leonid; Wheeler, Steven E.; Ticknor, Brian W.; Ahmed,Musahid; Leone, Stephen R.; Allen, Wesley D.; Schaefer III, Henry F.; Duncan, Michael A.
Dustbuster: a compact impact-ionization time-of-flight mass spectrometer for in situ analysis of cosmic dust
a large target area with a reflectron, simultaneously optimizing mass resolution, particle detection. The resulting ions, with broad energy and angular distributions, are accelerated through a modified reflectron remote sensing, collection and analysis of dust grains that have survived impact on the Earth, capture
Stewart, Sarah T.
Thermal Decomposition of Molecules Relevant to Combustion and Chemical Vapor Deposition by Flash Pyrolysis Time-of-Flight Mass Spectrometry
of Small Molecules by Flash Pyrolysis, University ofwas performed using flash pyrolysis vacuum-ultraviolet time-Vapor Deposition by Flash Pyrolysis Time-of-Flight Mass
Lemieux, Jessy Mario
Novel -Distonic Radical Cations [CnH2n+2S]+ (n ) 2, 3) Formed upon Decarbonylation of Ionized S-Alkyl Thioformates: A Mass Spectrometric and ab Initio Study
ions. Strong evidence for the distonic nature of the fragment ions derived from 2-7·+ has been obtained to intense peaks corresponding to H2S·+ and ionized olefins. Portions of the potential energy surface related explored in the gas phase by a variety of mass spectral methods.2,3 In particular, the -distonic isomer
Nguyen, Minh Tho
Laser ablation-inductively coupled plasma-mass spectrometry: Examinations of the origins of polyatomic ions and advances in the sampling of particulates
This dissertation provides a general introduction to Inductively coupled plasma-mass spectrometry (ICP-MS) and laser ablation (LA) sampling, with an examination of analytical challenges in the employment of this technique. It discusses the origin of metal oxide ions (MO+) in LA-ICP-MS, as well as the effect of introducing helium and nitrogen to the aerosol gas flow on the formation of these polyatomic interferences. It extends the study of polyatomic ions in LA-ICP-MS to metal argide (MAr+) species, an additional source of possible significant interferences in the spectrum. It describes the application of fs-LA-ICP-MS to the determination of uranium isotope ratios in particulate samples.
Witte, Travis
MANTRA: An Integral Reactor Physics Experiment to Infer Actinide Capture Cross-sections from Thorium to Californium with Accelerator Mass Spectrometry
The principle of the proposed experiment is to irradiate very pure actinide samples in the Advanced Test Reactor at INL and, after a given time, determine the amount of the different transmutation products. The determination of the nuclide densities before and after neutron irradiation will allow inference of effective neutron capture cross-sections. This approach has been used in the past and the novelty of this experiment is that the atom densities of the different transmutation products will be determined using the Accelerator Mass Spectrometry technique at the ATLAS facility located at ANL. It is currently planned to irradiate the following isotopes: 232Th, 235U, 236U, 238U, 237Np, 238Pu, 239Pu, 240Pu, 241Pu, 242Pu, 241Am, 243Am, 244Cm and 248Cm.
G. Youinou; C. McGrath; G. Imel; M. Paul; R. Pardo; F. Kondev; M. Salvatores; G. Palmiotti
Ion mass spectrometry investigations of the discharge during reactive high power pulsed and direct current magnetron sputtering of carbon in Ar and Ar/N{sub 2}
Ion mass spectrometry was used to investigate discharges formed during high power impulse magnetron sputtering (HiPIMS) and direct current magnetron sputtering (DCMS) of a graphite target in Ar and Ar/N{sub 2} ambient. Ion energy distribution functions (IEDFs) were recorded in time-averaged and time-resolved mode for Ar{sup +}, C{sup +}, N{sub 2}{sup +}, N{sup +}, and C{sub x}N{sub y}{sup +} ions. An increase of N{sub 2} in the sputter gas (keeping the deposition pressure, pulse width, pulse frequency, and pulse energy constant) results for the HiPIMS discharge in a significant increase in C{sup +}, N{sup +}, and CN{sup +} ion energies. Ar{sup +}, N{sub 2}{sup +}, and C{sub 2}N{sup +} ion energies, in turn, did not considerably vary with the changes in working gas composition. The HiPIMS process showed higher ion energies and fluxes, particularly for C{sup +} ions, compared to DCMS. The time evolution of the plasma species was analyzed for HiPIMS and revealed the sequential arrival of working gas ions, ions ejected from the target, and later during the pulse-on time molecular ions, in particular CN{sup +} and C{sub 2}N{sup +}. The formation of fullerene-like structured CN{sub x} thin films for both modes of magnetron sputtering is explained by ion mass-spectrometry results and demonstrated by transmission electron microscopy as well as diffraction.
Schmidt, S.; Greczynski, G.; Jensen, J.; Hultman, L. [Thin Film Physics Div., Department of Physics (IFM), Linkoeping University, SE-581 83 (Sweden); Czigany, Zs. [Institute of Technical Physics and Materials Science, Research Centre for Natural Sciences, Hungarian Academy of Sciences, Konkoly Thege Miklos ut 29-33. H-1121 Budapest (Hungary)
C-O-H ratios of silicate melt inclusions in basalts from the Galapagos spreading center near 95 degree W: A leaser decrepitation mass spectrometry study
Volatile ratios (primarily of H{sub 2}O and CO{sub 2}) in individual silicate melt (glass) inclusions in minerals have been analyzed using laser volatilization and mass spectrometry. A Nd-glass laser was used to produce 50-micrometer diameter pits in silicate melt inclusions. Released volatiles were analyzed directly with a computer-controlled quadrupole mass spectrometer. The mean CO{sub 2}/H{sub 2}O from the propagating rift (0.245 {plus minus} 0.068) silicate glass inclusions is significantly lower than that of the actively failing rift (0.641 {plus minus} 0.241); this difference probably reflects different degrees of degassing during contrasting magmatic histories for the two regions. Relatively undifferentiated failing rift magmas must have relatively short crustal residence time prior to eruption and, therefore, have not undergone significant degassing of CO{sub 2}, as would appear to be the case for the more highly fractionated propagating rift magmas. The laser-mass spectrometric system described herein has the ability to act as a point-source probing device that can differentiate between the various volatile sites in minerals and rocks (as well as synthetic materials) on a micrometer scale.
Yonover, R.N.; Sinton, J.M. (Univ. of Hawaii, Honolulu (USA)); Gibson, E.K. (NASA/Johnson Space Center, Houston, TX (USA)); Sommer, M.A.
High mass resolution time of flight mass spectrometer for measuring products in heterogeneous catalysis in highly sensitive microreactors
We demonstrate a combined microreactor and time of flight system for testing and characterization of heterogeneous catalysts with high resolution mass spectrometry and high sensitivity. Catalyst testing is performed in silicon-based microreactors which have high sensitivity and fast thermal response. Gas analysis is performed with a time of flight mass spectrometer with a modified nude Bayard-Alpert ionization gauge as gas ionization source. The mass resolution of the time of flight mass spectrometer using the ion gauge as ionization source is estimated to m/{Delta}m > 2500. The system design is superior to conventional batch and flow reactors with accompanying product detection by quadrupole mass spectrometry or gas chromatography not only due to the high sensitivity, fast temperature response, high mass resolution, and fast acquisition time of mass spectra but it also allows wide mass range (0-5000 amu in the current configuration). As a demonstration of the system performance we present data from ammonia oxidation on a Pt thin film showing resolved spectra of OH and NH{sub 3}.
Andersen, T.; Jensen, R.; Christensen, M. K.; Chorkendorff, I. [Department of Physics, Danish National Research Foundation's Center for Individual Nanoparticle Functionality (CINF), Technical University of Denmark, Building 312, DK-2800 Kgs. Lyngby (Denmark); Pedersen, T.; Hansen, O. [Department of Micro- and Nanotechnology, Technical University of Denmark, DTU Nanotech Building 345 East, DK-2800 Kgs. Lyngby (Denmark)
Advanced Mass Calibration and Visualization for FT-ICR Mass Spectromet...
for FT-ICR Mass Spectrometry Imaging. Abstract: Mass spectrometry imaging by Fourier transform ion cyclotron resonance (FT-ICR) yields hundreds of unique peaks, many of which...
Final Technical Report for DE-FG02-06ER15835: Chemical Imaging with 100nm Spatial Resolution: Combining High Resolution Flurosecence Microscopy and Ion Mobility Mass Spectrometry
We have combined, in a single instrument, high spatial resolution optical microscopy with the chemical specificity and conformational selectivity of ion mobility mass spectrometry. We discuss the design and construction of this apparatus as well as our efforts in applying this technique to thin films of molecular semiconductor materials.
Buratto, Steven K. [UC Santa Barbara
PILOT_PROTEIN: Identification of Unmodified and Modified Proteins via High-Resolution Mass Spectrometry and Mixed-Integer Linear
accuracy with a lower false positive rate. All materials are freely available to the scientific community and protein identification and can help reduce the number of false positive resulPILOT_PROTEIN: Identification of Unmodified and Modified Proteins via High-Resolution Mass
Shorter, James
and Ion Processes ELSEVIER International Journal of Mass Spectrometry and lon Processes 167/168 (1997) 637-647
/168 (1997) 637-647 Microsolvation of the ammonium ion in argon: infrared spectra of NH --Arn complexes (n Received 25 November 1996; accepted 2 June 1997 Abstract Infrared spectra of mass selected NH~-Ar, (n = 1 of the tetrahedral monomer. © 1997 Elsevier Science B.V. © 1997 Elsevier Science B.V. Keywords: Ab initio studies
Analysis on the Go: Quantitation of Drugs of Abuse in Dried Urine with Digital Microfluidics and Miniature Mass Spectrometry
Analysis on the Go: Quantitation of Drugs of Abuse in Dried Urine with Digital Microfluidics the development of a method coupling microfluidics and a miniature mass spectrometer, applied to quantitation of drugs of abuse in urine. A custom digital microfluidic system was designed to deliver droplets
Zandstra, Peter W.
Standard test method for analysis of urine for uranium-235 and uranium-238 isotopes by inductively coupled plasma-mass spectrometry
1.1 This test method covers the determination of the concentration of uranium-235 and uranium-238 in urine using Inductively Coupled Plasma-Mass Spectrometry. This test method can be used to support uranium facility bioassay programs. 1.2 This method detection limits for 235U and 238U are 6 ng/L. To meet the requirements of ANSI N13.30, the minimum detectable activity (MDA) of each radionuclide measured must be at least 0.1 pCi/L (0.0037 Bq/L). The MDA translates to 47 ng/L for 235U and 300 ng/L for 238U. Uranium� 234 cannot be determined at the MDA with this test method because of its low mass concentration level equivalent to 0.1 pCi/L. 1.3 The digestion and anion separation of urine may not be necessary when uranium concentrations of more than 100 ng/L are present. 1.4 Units�The values stated in picoCurie per liter units are to be regarded as standard. The values given in parentheses are mathematical conversions to SI units that are provided for information only and are not considered standard. 1....
Standard test method for analysis of isotopic composition of uranium in nuclear-grade fuel material by quadrupole inductively coupled plasma-mass spectrometry
1.1 This test method is applicable to the determination of the isotopic composition of uranium (U) in nuclear-grade fuel material. The following isotopic weight percentages are determined using a quadrupole inductively coupled plasma-mass spectrometer (Q-ICP-MS): 233U, 234U, 235U, 236U, and 238U. The analysis can be performed on various material matrices after acid dissolution and sample dilution into water or dilute nitric (HNO3) acid. These materials include: fuel product, uranium oxide, uranium oxide alloys, uranyl nitrate (UNH) crystals, and solutions. The sample preparation discussed in this test method focuses on fuel product material but may be used for uranium oxide or a uranium oxide alloy. Other preparation techniques may be used and some references are given. Purification of the uranium by anion-exchange extraction is not required for this test method, as it is required by other test methods such as radiochemistry and thermal ionization mass spectroscopy (TIMS). This test method is also described i...
Development of matrix assisted laser desorption ionization-ion mobility-orthogonal time-of-flight mass spectrometry as a tool for proteomics
-phase structural propensities for tryptic peptide ions. It is found that a small percentage (~3%) of peptide sequences form extended (i.e., helical or ?-sheet type) structures in the gas-phase, thus influencing the overall appearance area for peptide ions...
Ruotolo, Brandon Thomas
Studies on the dissociation reactions of [M + H]? and [M + A]? ions of small, model peptides using tandem mass spectrometry and fast atom bombardment ionization
10 Collision-induced dissociation (CID) spectrum of the [M + H]+ ious of arg-gly Collision-induced dissociation (CID) spectrum of the [M + Na]+ ions of arg-gly . 27 29 12 13 Collision-induced dissociation (CID) the [M + Li]+ ions ol' arg... the relative abundances of the [a + H]+ ions. Admixing a sodium source with solid samples of amino acids did not increase the relative 10 abundance of the [a + Na]+ ions. In fact, addition of a solid amino acid decreased the relative abundance, since...
McGlohon, Elizabeth Scott
Electronic structure and spectroscopy of nucleic acid bases: Ionization energies, ionization-induced structural changes, and photoelectron spectra
We report high-level ab initio calculations and single-photon ionization mass spectrometry study of ionization of adenine (A), thymine (T), cytosine (C) and guanine (G). For thymine and adenine, only the lowest-energy tautomers were considered, whereas for cytosine and guanine we characterized five lowest-energy tautomeric forms. The first adiabatic and several vertical ionization energies were computed using equation-of-motion coupled-cluster method for ionization potentials with single and double substitutions. Equilibrium structures of the cationic ground states were characterized by DFT with the {omega}B97X-D functional. The ionization-induced geometry changes of the bases are consistent with the shapes of the corresponding molecular orbitals. For the lowest-energy tautomers, the magnitude of the structural relaxation decreases in the following series G > C > A > T, the respective relaxation energies being 0.41, 0.32, 0.25 and 0.20 eV. The computed adiabatic ionization energies (8.13, 8.89, 8.51-8.67 and 7.75-7.87 eV for A,T,C and G, respectively) agree well with the onsets of the photoionization efficiency (PIE) curves (8.20 {+-} 0.05, 8.95 {+-} 0.05, 8.60 {+-} 0.05 and 7.75 {+-} 0.05 eV). Vibrational progressions for the S{sub 0}-D{sub 0} vibronic bands computed within double-harmonic approximation with Duschinsky rotations are compared with previously reported experimental photoelectron spectra.
Bravaya, Ksenia B.; Kostko, Oleg; Dolgikh, Stanislav; Landau, Arie; Ahmed, Musahid; Krylov, Anna I.
Charge and frequency resolved isochronous mass spectrometry in storage rings: First direct mass measurement of the short-lived neutron-deficient $^{51}$Co nuclide
Revolution frequency measurements of individual ions in storage rings require sophisticated timing detectors. One of common approaches for such detectors is the detection of secondary electrons released from a thin foil due to penetration of the stored ions. A new method based on the analysis of intensities of secondary electrons was developed which enables determination of the charge of each ion simultaneously with the measurement of its revolution frequency. Although the mass-over-charge ratios of $^{51}$Co$^{27+}$ and $^{34}$Ar$^{18+}$ ions are almost identical, and therefore, the ions can not be resolved in a storage ring, by applying the new method the mass excess of the short-lived $^{51}$Co is determined for the first time to be ME($^{51}$Co)=-27342(48) keV. Shell-model calculations in the $fp$-shell nuclei compared to the new data indicate the need to include isospin-nonconserving forces.
P. Shuai; H. S. Xu; X. L. Tu; Y. H. Zhang; B. H. Sun; Yu. A. Litvinov; X. L. Yan; K. Blaum; M. Wang; X. H. Zhou; J. J. He; Y. Sun; K. Kaneko; Y. J. Yuan; J. W. Xia; J. C. Yang; G. Audi; X. C. Chen; G. B. Jia; Z. G. Hu; X. W. Ma; R. S. Mao; B. Mei; Z. Y. Sun; S. T. Wang; G. Q. Xiao; X. Xu; T. Yamaguchi; Y. Yamaguchi; Y. D. Zang; H. W. Zhao; T. C. Zhao; W. Zhang; W. L. Zhan
Investigation of ionized metal flux in enhanced high power impulse magnetron sputtering discharges
The metal ionized flux fraction and production of double charged metal ions Me{sup 2+} of different materials (Al, Cu, Fe, Ti) by High Power Impulse Magnetron Sputtering (HiPIMS) operated with and without a pre-ionization assistance is compared in the paper. The Electron Cyclotron Wave Resonance (ECWR) discharge was employed as the pre-ionization agent providing a seed of charge in the idle time of HiPIMS pulses. A modified grid-free biased quartz crystal microbalance was used to estimate the metal ionized flux fraction ?. The energy-resolved mass spectrometry served as a complementary method to distinguish particular ion contributions to the total ionized flux onto the substrate. The ratio between densities of doubly Me{sup 2+} and singly Me{sup +} charged metal ions was determined. It is shown that ECWR assistance enhances Me{sup 2+} production with respect of absorbed rf-power. The ECWR discharge also increases the metal ionized flux fraction of about 30% especially in the region of lower pressures. Further, the suppression of the gas rarefaction effect due to enhanced secondary electron emission of Me{sup 2+} was observed.
Stranak, Vitezslav, E-mail: email@example.com [Faculty of Science, University of South Bohemia, Branisovska 31, 37005 Ceske Budejovice (Czech Republic); Hubicka, Zdenek; Cada, Martin [Institute of Physics v. v. i., Academy of Science of the Czech Republic, Na Slovance 2, 182 21 Prague (Czech Republic); Drache, Steffen; Hippler, Rainer [Institut f�r Physik, Ernst-Moritz-Arndt-Universit�t Greifswald, Felix-Hausdorff-Str. 6, 17489 Greifswald (Germany); Tichy, Milan [Faculty of Mathematics and Physics, Charles University in Prague, V Holesovickach 2, 180 00 Prague (Czech Republic)
Identification of protein-protein interaction and topologies in living cells by chemical cross-linking and mass spectrometry
Current chemical cross-linking methods are commonly employed for mapping sites of interaction and three-dimensional structure in purified, known protein complexes. When applied in vivo in combination of co-immunoprecipitation methods, information on the sites of interaction between proteins are unattainable due to overwhelming sample complexity. We present results from a novel cross-linking strategy that allow simultaneous protein-protein interaction and surface topology measurement in vivo without any prior knowledge of the system. The strategy consists of: (i) cross-linking reaction: intact cell labeling with protein interaction reporters (PIRs); (ii) two-stage mass spectrometric analysis: stage 1 identification of PIR-labeled proteins and construction of a restricted database by 2D-LC/MS/MS; and stage 2 analysis of PIR-labeled peptides by multiplexed LC/FTICR-MS; (iii) data analysis: identification of cross-linked peptides and proteins of origin using accurate mass and other constraints. This strategy was applied to Shewanella oneidensis MR-1 bacterial cells and successfully identified a protein-protein interaction between SecA and a small outer membrane lipoprotein as well as their sites of interaction in vivo.
Zhang, Haizhen; Tang, Xiaoting; Munske, Gerhard R.; Tolic, Nikola; Anderson, Gordon A.; Bruce, James E.
Identification of Protein-Protein Interactions and Topologies in Living Cells with Chemical Cross-linking and Mass Spectrometry
We present results from a novel strategy that enables concurrent identification of protein-protein interactions and topologies in living cells without specific antibodies or genetic manipulations for immuno/affinity purifications. The strategy consists of: (i) chemical cross-linking reaction: intact cell labeling with a novel class of chemical cross-linkers, protein interaction reporters (PIRs); (ii) two-stage mass spectrometric analysis: stage 1 identification of PIR-labeled proteins and construction of a restricted database by 2D-LC/MS/MS; and stage 2 analysis of PIR-labeled peptides by multiplexed LC/FTICR-MS; (iii) data analysis: identification of cross-linked peptides and proteins of origin using accurate mass and other constraints. The primary advantage of the PIR approach and distinction from current technology is that protein interactions together with topologies are detected in native biological systems by stabilizing protein complexes with new covalent bonds while the proteins are present in the original cellular environment. Thus, weak or transient interactions or interactions that require properly folded, localized, or membrane-bound proteins can be labeled and identified through the PIR approach. This strategy was applied to S. oneidensis bacterial cells and initial studies resulted in identification of a set of protein-protein interactions and their contact/binding regions. Furthermore, most identified interactions involved membrane proteins, suggesting the PIR approach is particularly suited for studies of membrane protein-protein interactions, an area under-represented with current widely-used approaches.
Retrieval of DNA using soft-landing after mass analysis by ESI-FTICR for enzymatic manipulation
The DNA modifications that lead to mutations are of direct interest for, e.g. the understanding of DNA damage recognition and repair. The characterization of the modified oligonucleotides and enzymatic responses to specific DNA modifications are of primary concern, but also present major analytical challenges. Among the available techniques, mass spectrometry has become an increasingly important tool for the study of oligonucleotides, their mutations, and interactions. Conventionally, mass spectrometry provides mass and structural information (e.g. from dissociation experiments and the use of tandem mass spectrometry). However, the small quantities of material analyzed and the destructive nature of conventional mass spectrometric detection (e.g., due to high energy impact on particle multiplier surfaces) have precluded subsequent use of mass separated biopolymers. The authors report the use of mass spectrometry in conjunction with soft-landing for the high-resolution analysis, separation, and selective collection of oligonucleotides, and their subsequent retrieval for enzymatic manipulation. Fourier transform ion cyclotron resonance mass spectrometry coupled with electrospray ionization (ESI-FTICR) allows nondestructive (i.e., image current) measurement of the mass-to-charge ratios (m/z) of ions with high sensitivity, resolution, and mass accuracy.
Feng, B.; Wunschel, D.S.; Masselon, C.D.; Pasa-Tolic, L.; Smith, R.D.
Design and performance of a combined secondary ion mass spectrometry-scanning probe microscopy instrument for high sensitivity and high-resolution elemental three-dimensional analysis
State-of-the-art secondary ion mass spectrometry (SIMS) instruments allow producing 3D chemical mappings with excellent sensitivity and spatial resolution. Several important artifacts however arise from the fact that SIMS 3D mapping does not take into account the surface topography of the sample. In order to correct these artifacts, we have integrated a specially developed scanning probe microscopy (SPM) system into a commercial Cameca NanoSIMS 50 instrument. This new SPM module, which was designed as a DN200CF flange-mounted bolt-on accessory, includes a new high-precision sample stage, a scanner with a range of 100 {mu}m in x and y direction, and a dedicated SPM head which can be operated in the atomic force microscopy (AFM) and Kelvin probe force microscopy modes. Topographical information gained from AFM measurements taken before, during, and after SIMS analysis as well as the SIMS data are automatically compiled into an accurate 3D reconstruction using the software program 'SARINA,' which was developed for this first combined SIMS-SPM instrument. The achievable lateral resolutions are 6 nm in the SPM mode and 45 nm in the SIMS mode. Elemental 3D images obtained with our integrated SIMS-SPM instrument on Al/Cu and polystyrene/poly(methyl methacrylate) samples demonstrate the advantages of the combined SIMS-SPM approach.
Wirtz, Tom; Fleming, Yves; Gerard, Mathieu [Department 'Science and Analysis of Materials' (SAM), Centre de Recherche Public, Gabriel Lippmann, 41 rue du Brill, L-4422 Belvaux (Luxembourg); Gysin, Urs; Glatzel, Thilo; Meyer, Ernst [Department of Physics, Universitaet Basel, Klingelbergstrasse 82, CH-4056 Basel (Switzerland); Wegmann, Urs [Department of Physics, Universitaet Basel, Klingelbergstrasse 82, CH-4056 Basel (Switzerland); Ferrovac GmbH, Thurgauerstr. 72, CH-8050 Zuerich (Switzerland); Maier, Urs [Ferrovac GmbH, Thurgauerstr. 72, CH-8050 Zuerich (Switzerland); Odriozola, Aitziber Herrero; Uehli, Daniel [SPECS Zurich GmbH, Technoparkstr. 1, CH-8005 Zuerich (Switzerland)
Soluble arsenic and selenium species in fly ash/organic waste-amended soils using ion chromatography-inductively coupled plasma mass spectrometry
Mixing coal fly ash with an organic waste increases macronutrient content and may make land application of fly ash a viable disposal alternative. However, trace element chemistry of these mixed waste products warrants investigation. Speciation of As and Se in soil solutions of fly ash-, poultry litter- and sewage sludge-amended soils was determined over a 10-day period by ion chromatography coupled to inductively coupled plasma mass spectrometry (IC-ICP-MS). Detection limits were 0.031, 0.028, 0.051, 0.161, 0.497, and 0.660 {micro}g L{sup {minus}1} for dimethylarsinate (DMA), As(III), monomethylarsonate (MMA), As(V), Se(IV), and Se(VI), respectively. Arsenic was highly water-soluble from poultry litter and appeared to be predominantly As(V). Arsenic(V) was the predominant species in soil amended with two fly ashes. Application of fly ash/poultry litter mixtures increased As solubility and led to the prevalence of DMA as the major As species. DMA concentrations of these soil solutions decreased rapidly over the sampling period relative to As(V), suggesting that DMA readily underwent mineralization in the soil solution. Se(VI) was the predominant soluble Se species in all treatments indicating rapid oxidation of Se(IV) initially solubilized from the fly ashes.
Jackson, B.P.; Miller, W.P. [Univ. of Georgia, Athens, GA (United States). Dept. of Crop and Soil Sciences] [Univ. of Georgia, Athens, GA (United States). Dept. of Crop and Soil Sciences
Identification of volatile butyl rubber thermal-oxidative degradation products by cryofocusing gas chromatography/mass spectrometry (cryo-GC/MS).
Chemical structure and physical properties of materials, such as polymers, can be altered as aging progresses, which may result in a material that is ineffective for its envisioned intent. Butyl rubber formulations, starting material, and additives were aged under thermal-oxidative conditions for up to 413 total days at up to 124 %C2%B0C. Samples included: two formulations developed at Kansas City Plant (KCP) (%236 and %2310), one commercially available formulation (%2321), Laxness bromobutyl 2030 starting material, and two additives (polyethylene AC-617 and Vanax MBM). The low-molecular weight volatile thermal-oxidative degradation products that collected in the headspace over the samples were preconcentrated, separated, and detected using cryofocusing gas chromatography mass spectrometry (cryo-GC/MS). The majority of identified degradation species were alkanes, alkenes, alcohols, ketones, and aldehydes. Observations for Butyl %2310 aged in an oxygen-18 enriched atmosphere (18O2) were used to verify when the source of oxygen in the applicable degradation products was from the gaseous environment rather than the polymeric mixture. For comparison purposes, Butyl %2310 was also aged under non-oxidative thermal conditions using an argon atmosphere.
Smith, Jonell Nicole; White, Michael Irvin; Bernstein, Robert; Hochrein, James Michael
Gadolinium speciation with Tetradentate, N-donor extractants for minor actinide/lanthanide separation: an XRD, mass spectrometry and EPR study
The hydrophobic organic molecules CyMe{sub 4}-BTPhen (1) and CyMe{sub 4}-BTBP (2) have been developed and tuned over many years to be able to separate the trivalent actinides from the trivalent lanthanides (Ln) selectively in bi-phasic solvent extraction processes for the separation of the long-lived radio-toxic minor actinides from spent nuclear fuel. The ability of these N-donor ligands to perform this separation is poorly understood, as is their speciation with the metal ions when extracted into the organic phase. Our previous work has shown Ln{sup 3+} speciation to be largely 1:2 Ln:L in nature with another small molecule, either water or nitrate, occupying a cavity between the tetradentate bound N-donor ligands. The identity of the small molecule changes across the lanthanide series, and here we continue investigations into this speciation. Complexes of these N-donor ligands with Gd{sup 3+} have been synthesised and characterised by X-ray crystallography, mass spectrometry and EPR spectroscopy. We show that the N-donor ligands have no effect on the electronic configuration of Gd{sup 3+} and that the lanthanide contraction with the steric rigidity of the N-donor ligand appears to determine the size of the cavity between the coordinated ligands. This in turn appears to control the identity of the small molecule on the ninth site in the 1:2 Gd:L species. (authors)
Whittaker, D.M. [School of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL (United Kingdom); Sharrad, C.A. [School of Chemical Engineering and Analytical Science, The University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom); Research Centre for Radwaste and Decommissioning, Dalton Nuclear Institute, The University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom); Sproules, S. [Photon Science Institute, The University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom); WestCHEM, School of Chemistry, University of Glasgow, Glasgow G12 8QQ (United Kingdom)
Analysis of Nitro-Polycyclic Aromatic Hydrocarbons in Conventional Diesel and Fischer--Tropsch Diesel Fuel Emissions Using Electron Monochromator-Mass Spectrometry
The presence of nitro-polycyclic aromatic hydrocarbons (NPAHs) in diesel fuel emissions has been studied for a number of years predominantly because of their contribution to the overall health and environmental risks associated with these emissions. Electron monochromator-mass spectrometry (EM-MS) is a highly selective and sensitive method for detection of NPAHs in complex matrixes, such as diesel emissions. Here, EM-MS was used to compare the levels of NPAHs in fuel emissions from conventional (petroleum) diesel, ultra-low sulfur/low-aromatic content diesel, Fischer-Tropsch synthetic diesel, and conventional diesel/synthetic diesel blend. The largest quantities of NPAHs were detected in the conventional diesel fuel emissions, while the ultra-low sulfur diesel and synthetic diesel fuel demonstrated a more than 50% reduction of NPAH quantities when compared to the conventional diesel fuel emissions. The emissions from the blend of conventional diesel with 30% synthetic diesel fuel also demonstrated a more than 30% reduction of the NPAH content when compared to the conventional diesel fuel emissions. In addition, a correlation was made between the aromatic content of the different fuel types and NPAH quantities and between the nitrogen oxides emissions from the different fuel types and NPAH quantities. The EM-MS system demonstrated high selectivity and sensitivity for detection of the NPAHs in the emissions with minimal sample cleanup required.
Havey, C. D.; McCormick, R. L.; Hayes, R. R.; Dane, A. J.; Voorhees, K. J.
Ionization chamber
An ionization chamber has separate drift and detection regions electrically isolated from each other by a fine wire grid. A relatively weak electric field can be maintained in the drift region when the grid and another electrode in the chamber are connected to a high voltage source. A much stronger electric field can be provided in the detection region by connecting wire electrodes therein to another high voltage source. The detection region can thus be operated in a proportional mode when a suitable gas is contained in the chamber. High resolution output pulse waveforms are provided across a resistor connected to the detection region anode, after ionizing radiation enters the drift region and ionize the gas.
Walenta, Albert H. (Port Jefferson Station, NY)
Studies of the combustion of coal/refuse derived fuels using thermogravimetric-Fourier transform infrared-mass spectrometry
The materials used in this project included two bituminous coals, a medium molecular weight PVC resin, cellulose, and shredded newspaper. Analytical data for the samples are given. A TA Instruments Model 951 Thermogravimetric Analyzer (TG) interfaced to a Perkin Elmer 1650 Fourier Transform Infrared Spectrometer (FTIR) was used in this study. The horizontal quartz furnace of the TG was connected to the 10 cm gas cell of the FTIR using an insulated teflon tube heated to a temperature of 150{degrees}C. The TG was also interfaced to a VG Thermolab Mass Spectrometer (MS) using a fused silica capillary sampling tube heated to approximately 170{degrees}C. A teflon splitter divides the gases from the TG into two parts, one to the FTIR ({approximately}95%), and the other to the MS ({approximately}5%). A schematic of the TG-FTIR-MS system, is presented. In the TG experiments, all samples ({approximately}300 mg each) were heated in air (50 ML/min) at a rate of 10{degrees}C/min to 700{degrees}C. The spectra and profiles of gaseous species evolving from the TG system were recorded and analyzed by the TGA-FTIR-MS analytical system. The results of the experiments are given.
Lu, H.; Li, J.; Lloyd, W.G. [and others
C60 Secondary Ion Fourier Transform Ion Cyclotron Resonance Mass...
C60 Secondary Ion Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. C60 Secondary Ion Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. Abstract: Secondary...
A Hybrid Approach to Protein Differential Expression in Mass...
Hybrid Approach to Protein Differential Expression in Mass Spectrometry-Based Proteomics. A Hybrid Approach to Protein Differential Expression in Mass Spectrometry-Based...
Investigating Enhanced Thorium Ionization in TIMS Using Re/Pt Porous Ion Emitters
Thermal ionization mass spectrometry (TIMS) is a widely used, benchmark method in the isotopic analysis of actinides relevant to various nuclear and geological fields. Despite significant previous use and inherent advantages, however, poor sample ionization continues to hamper the use of TIMS in the measurement of trace species; actinide ionization efficiencies frequently fall below 0.1 % using traditional instrument sources. Factors leading to poor ionization are compounded in the measurement of several highly refractory metals (e.g. U and Th) that may provide key signatures data in non-proliferation, safeguards and forensics efforts. Herein, a relatively new TIMS ion source strategy, employing porous ion emitters (PIEs) atop traditional filament assemblies, is investigated for the first time as a straightforward means of enhancing the ionization of Th, which is arguably a worst case scenario for TIMS-based actinide measurements. These sources yielded up to 410% greater Th sample utilization, relative to previously published values and in-house measurements collected using traditional methods. Accompanying scanning electron microscopy (SEM) investigations provide preliminary insight into possible mechanisms of PIE functioning and explore the impacts that extended heating have on the constructed source�s structure and composition.
Floyd E. Stanley III; K. J. Spencer; D. S. Schwartz; M. G. Watrous; J. E. Delmore
Tile-Based Fisher-Ratio Software for Improved Feature Selection Analysis of Comprehensive Two-Dimensional Gas Chromatography Time-of-Flight Mass Spectrometry Data
Two-dimensional (2D) gas chromatography coupled with time-of-flight mass spectrometry (GC � GC � TOFMS) is a highly capable instrumental platform that produces complex and information-rich multi-dimensional chemical data. The complex data can be overwhelming, especially when many samples (of various sample classes) are analyzed with multiple injections for each sample. Thus, the data must be analyzed in such a way to extract the most meaningful information. The pixel-based and peak table-based algorithmic use of Fisher ratios has been used successfully in the past to reduce the multi-dimensional data down to those chemical compounds that are changing between classes relative to those that are not (i.e., chemical feature selection). We report on the initial development of a computationally fast novel tile-based Fisher-ratio software that addresses challenges due to 2D retention time misalignment without explicitly aligning the data, which is a problem for both pixel-based and peak table- based methods. Concurrently, the tile-based Fisher-ratio software maximizes the sensitivity contrast of true positives against a background of potential false positives and noise. To study this software, eight compounds, plus one internal standard, were spiked into diesel at various concentrations. The tile-based F-ratio software was able to discover all spiked analytes, within the complex diesel sample matrix with thousands of potential false positives, in each possible concentration comparison, even at the lowest absolute spiked analyte concentration ratio of 1.06.
Marney, Luke C.; Siegler, William C.; Parsons, Brendon A.; Hoggard, Jamin C.; Wright, Bob W.; Synovec, Robert E.
Rapid and sensitive gas chromatography ion-trap mass spectrometry method for the determination of tobacco specific N-nitrosamines in secondhand smoke
Tobacco-specific nitrosamines (TSNAs) are some of the most potent carcinogens in tobacco and cigarette smoke. Accurate quantification of these chemicals is needed to help assess public health risks. We developed and validated a specific and sensitive method to measure four TSNAs in both the gas- and particle-phase of secondhand smoke (SHS) using gas chromatography and ion-trap tandem mass spectrometry,. A smoking machine in an 18-m3 room-sized chamber generated relevant concentrations of SHS that were actively sampled on Teflon coated fiber glass (TCFG) filters, and passively sampled on cellulose substrates. A simple solid-liquid extraction protocol using methanol as solvent was successfully applied to both filters with high recoveries ranging from 85 to 115percent. Tandem MS parameters were optimized to obtain the best sensitivity in terms of signal to-noise ratio (S/N) for the target compounds. For each TSNA, the major fragmentation pathways as well as ion structures were elucidated and compared with previously published data. The method showed excellent performances with a linear dynamic range between 2 and 1000 ng mL-1, low detection limits (S/N> 3) of 30-300 pg.ml-1 and precision with experimental errors below 10percent for all compounds. Moreover, no interfering peaks were observed indicating a high selectivity of MS/MS without the need for a sample clean up step. The sampling and analysis method provides a sensitive and accurate tool to detect and quantify traces of TSNA in SHS polluted indoor environments.
SLEIMAN, Mohamad; MADDALENA, Randy L.; GUNDEL, Lara A.; DESTAILLATS, Hugo
Targeted Peptide Measurements in Biology and Medicine: Best Practices for Mass Spectrometry-based Assay Development Using a Fit-for-Purpose Approach
Adoption of targeted mass spectrometry (MS) approaches such as multiple reaction monitoring (MRM) to study biological and biomedical questions is well underway in the proteomics community. Successful application depends on the ability to generate reliable assays that uniquely and confidently identify target peptides in a sample. Unfortunately, there is a wide range of criteria being applied to say that an assay has been successfully developed. There is no consensus on what criteria are acceptable and little understanding of the impact of variable criteria on the quality of the results generated. Publications describing targeted MS assays for peptides frequently do not contain sufficient information for readers to establish confidence that the tests work as intended or to be able to apply the tests described in their own labs. Guidance must be developed so that targeted MS assays with established performance can be made widely distributed and applied by many labs worldwide. To begin to address the problems and their solutions, a workshop was held at the National Institutes of Health with representatives from the multiple communities developing and employing targeted MS assays. Participants discussed the analytical goals of their experiments and the experimental evidence needed to establish that the assays they develop work as intended and are achieving the required levels of performance. Using this �fit-for-purpose� approach, the group defined three tiers of assays distinguished by their performance and extent of analytical characterization. Computational and statistical tools useful for the analysis of targeted MS results were described. Participants also detailed the information that authors need to provide in their manuscripts to enable reviewers and readers to clearly understand what procedures were performed and to evaluate the reliability of the peptide or protein quantification measurements reported. This paper presents a summary of the meeting and recommendations. Molecular & Cellular Proteomics 13: 10.1074/mcp.M113.036095, 907�917, 2014.
Carr, Steven A.; Abbateillo, Susan E.; Ackermann, Bradley L.; Borchers, Christoph H.; Domon, Bruno; Deutsch, Eric W.; Grant, Russel; Hoofnagle, Andrew N.; Huttenhain, Ruth; Koomen, John M.; Liebler, Daniel; Liu, Tao; MacLean, Brendan; Mani, DR; Mansfield, Elizabeth; Neubert, Hendrik; Paulovich, Amanda G.; Reiter, Lukas; Vitek, Olga; Aebersold, Ruedi; Anderson, Leigh N.; Bethem, Robert; Blonder, Josip; Boja, Emily; Botelho, Julianne; Boyne, Michael; Bradshaw, Ralph A.; Burlingame, Alma S.; Chan, Daniel W.; Keshishian, Hasmik; Kuhn, Eric; Kingsinger, Christopher R.; Lee, Jerry S.; Lee, Sang-Won; Moritz, Robert L.; Oses-Prieto, Juan; Rifai, Nader; Ritchie, James E.; Rodriguez, Henry; Srinivas, Pothur R.; Townsend, Reid; Van Eyk , Jennifer; Whiteley, Gordon; Wiita, Arun; Weintraub, Susan
Sandia National Laboratories: mass spectrometry
AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE:1 First Use of Energy for All Purposes (Fuel and Nonfuel),Feet) Year Jan Feb Mar Apr MayAtmosphericNuclear Security Administration the1developmentturbine bladelifetime is the cumulative time underpower measurementmass
Quantification of absorption, retention and elimination of two different oral doses of vitamin A in Zambian boys using accelerator mass spectrometry
A recent survey indicated that high-dose vitamin A supplements (HD-VAS) had no apparent effect on vitamin A (VA) status of Zambian children <5 y of age. To explore possible reasons for the lack of response to HD-VAS among Zambian children, we quantified the absorption, retention, and urinary elimination of either a single HDVAS (60 mg) or a smaller dose of stable isotope (SI)-labeled VA (5 mg), which was used to estimate VA pool size, in 3-4 y old Zambian boys (n = 4 for each VA dose). A 25 nCi tracer dose of [{sup 14}C{sub 2}]-labeled VA was co-administered with the HD-VAS or SI-labeled VA, and 24-hr stool and urine samples were collected for 3 and 7 consecutive days, respectively, and 24-hr urine samples at 4 later time points. Accelerator Mass Spectrometry (AMS) was used to measure the cumulative excretion of {sup 14}C in stool and urine 3d after dosing to estimate, respectively, absorption and retention of the VAS and SI-labeled VA. The urinary elimination rate (UER) was estimated by plotting {sup 14}C in urine vs. time, and fitting an exponential equation to the data. Estimates of mean absorption, retention and the UER were 83.8 {+-} 7.1%, 76.3 {+-} 6.7%, and 1.9 {+-} 0.6%/d, respectively, for the HD-VAS and 76.5 {+-} 9.5%, 71.1 {+-} 9.4%, and 1.8 {+-} 1.2%/d, respectively for the smaller dose of SI-labeled VA. Estimates of absorption, retention and the UER did not differ by size of the VA dose administered (P=0.26, 0.40, 0.88, respectively). Estimated absorption and retention were negatively associated with reported fever (P=0.011) and malaria (P =0.010). HD-VAS and SI-labeled VA were adequately absorbed, retained and utilized in apparently healthy Zambian preschool-age boys, although absorption and retention may be affected by recent infections.
Aklamati, E K; Mulenga, M; Dueker, S R; Buchholz, B A; Peerson, J M; Kafwembe, E; Brown, K H; Haskell, M J
Direct evidence of a strong isomer effect in electron-impact double ionization of C{sub 3}H{sub 4}
The electron-impact double ionization of two isomers of C{sub 3}H{sub 4} (allene and propyne) between 25 and 1000 eV has been investigated using time-of-flight mass spectrometry. Unambiguous differences in the partial double-ionization spectra of these isomers are observed over the entire energy range. These isomer effects have been observed in C{sub 3}H{sub 4} through the recording of target product channels and, in particular, when hard collisions involving the transfer of a large amount of energy is involved. Measurements of double-ionization events which fragment through Coulomb explosion are also reported. Coincidences between the charged fragment ions and protons were measured and shown to only exhibit isomer effects in the channel involving production of H{sup +}+CH{sub 2}{sup +}.
Scully, S.W.J.; Senthil, V.; Wyer, J.A.; Shah, M.B.; Montenegro, E.C.; Kimura, M.; Tawara, H. [Department of Physics and Astronomy, Queen's University Belfast, Belfast BT7 1NN (United Kingdom); Department of Chemistry, Graduate School of Science, Kyushu University, Hakozaki, Fukuoka 812-8581 (Japan); Max Planck Institute of Nuclear Physics, Saupfercheckweg 1, D-69117 Heidelberg (Germany)
EMSL - Mass Spectrometer
MS) with high mass resolution (m&61636;m100,000). Solvent mixtures of acetonitrilewater and acetonitriletoluene were used to extract and ionize polar and non-polar...
Atmospheric sampling glow discharge ionization source
An atmospheric sampling glow discharge ionization source that can be used in combination with an analytical instrument which operates at high vacuum, such as a mass spectrometer. The atmospheric sampling glow discharge ionization source comprises a chamber with at least one pair of electrodes disposed therein, an inlet for a gaseous sample to be analyzed and an outlet communicating with an analyzer which operates at subatmospheric pressure. The ionization chamber is maintained at a pressure below atmospheric pressure, and a voltage difference is applied across the electrodes to induce a glow discharge between the electrodes, so that molecules passing through the inlet are ionized by the glow discharge and directed into the analyzer. The ionization source accepts the sample under atmospheric pressure conditions and processes it directly into the high vacuum instrument, bridging the pressure gap and drawing off unwanted atmospheric gases. The invention also includes a method for analyzing a gaseous sample using the glow discharge ionization source described above. 3 figs.
McLuckey, S.A.; Glish, G.L.
atmospheric pressure ionization: Topics by E-print Network
for Atmospheric Pressure, in Vivo, and Imaging Mass. For example, atmospheric pressure infrared MALDI (AP IR-MALDI), capable of producing ions from small ionization (DESI),5...
Calculation of Transactinide Homolog Isotope Production Reactions Possible with the Center for Accelerator Mass Spectrometry (CAMS) at Lawrence Livermore National Laboratory
The LLNL heavy element group has been investigating the chemical properties of the heaviest elements over the past several years. The properties of the transactinides (elements with Z > 103) are often unknown due to their low production rates and short half-lives, which require lengthy cyclotron irradiations in order to make enough atoms for statistically significant evaluations of their chemistry. In addition, automated chemical methods are often required to perform consistent and rapid chemical separations on the order of minutes for the duration of the experiment, which can last from weeks to months. Separation methods can include extraction chromatography, liquid-liquid extraction, or gas-phase chromatography. Before a lengthy transactinide experiment can be performed at an accelerator, a large amount of preparatory work must be done both to ensure the successful application of the chosen chemical system to the transactinide chemistry problem being addressed, and to evaluate the behavior of the lighter elemental homologs in the same chemical system. Since transactinide chemistry is literally performed on one single atom, its chemical properties cannot be determined from bulk chemical matrices, but instead must be inferred from the behavior of the lighter elements that occur in its chemical group and in those of its neighboring elements. By first studying the lighter group homologs in a particular chemical system, when the same system is applied to the transactinide element under investigation, its decay properties can be directly compared to those of the homologues, thereby allowing an inference of its own chemistry. The Center for Accelerator Mass Spectrometry (CAMS) at Lawrence Livermore National Laboratory (LLNL) includes a 1 MV Tandem accelerator, capable of accelerating light ions such as protons to energies of roughly 15 MeV. By using the CAMS beamline, tracers of transactinide homolog elements can be produced both for development of chemical systems and for evaluation of homolog chemical properties. CAMS also offers an environment for testing these systems 'online' by incorporating automated chemical systems into the beamline so that tracers can be created, transported, and chemically separated all on the shorter timescales required for transactinide experiments. Even though CAMS is limited in the types and energies of ions they can accelerate, there are still a wide variety of reactions that can be performed there with commercially available target materials. The half-lives of these isotopes vary over a range that could be used for both online chemistry (where shorter half-lives are required) and benchtop tracers studies (where longer lived isotopes are preferred). In this document, they present a summary of tracer production reactions that could be performed at CAMS, specifically for online, automated chemical studies. They are from chemical groups four through seven, 13, and 14, which would be appropriate for studies of elements 104-107, 113, and 114. Reactions were selected that had (a) commercially available target material, (b) half-lives long enough for transport from a target chamber to an automated chemistry system, and (c) cross-sections at CAMS available projectile energies that were large enough to produce enough atoms to result in a statistically relevant signal after losses for transport and chemistry were considered. In addition, the resulting product atoms had to decay with an observable gamma-ray using standard Ge gamma-ray detectors. The table includes calculations performed for both metal targets and their corresponding oxides.
Moody, K J; Shaughnessy, D A; Gostic, J M
Current developments in laser ablation-inductively coupled plasma-mass spectrometry for use in geology, forensics, and nuclear nonproliferation research
This dissertation focused on new applications of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The diverse fields that were investigated show the versatility of the technique. In Chapter 2, LA-ICP-MS was used to investigate the rare earth element (REE) profiles of garnets from the Broken Hill Deposit in New South Wales, Australia. The normalized REE profiles helped to shed new light on the formation of deposits of sulfide ores. This information may be helpful in identifying the location of sulfide ore deposits in other locations. New sources of metals such as Pg, Zn, and Ag, produced from these ores, are needed to sustain our current technological society. The application of LA-ICP-MS presented in Chapter 3 is the forensics analysis of automotive putty and caulking. The elemental analysis of these materials was combined with the use of Principal Components Analysis (PCA). The PCA comparison was able to differentiate the automotive putty samples by manufacturer and lot number. The analysis of caulk was able to show a differentiation based on manufacturer, but no clear differentiation was shown by lot number. This differentiation may allow matching of evidence in the future. This will require many more analyses and the construction of a database made up of many different samples. The 4th chapter was a study of the capabilities of LA-ICP-MS for fast and precise analysis of particle ensembles for nuclear nonproliferation applications. Laser ablation has the ability to spatially resolve particle ensembles which may contain uranium or other actinides from other particles present in a sample. This is of importance in samples obtained from air on filter media. The particle ensembles of interest may be mixed in amongst dust and other particulates. A problem arises when ablating these particle ensembles directly from the filter media. Dust particles other than ones of interest may be accidentally entrained in the aerosol of the ablated particle ensemble. This would cause the analysis to be skewed. The use of a gelatin substrate allows the ablation a particle ensemble without disturbing other particles or the gelatin surface. A method to trap and ablate particles on filter paper using collodion was also investigated. The laser was used to dig through the collodion layer and into the particle ensemble. Both of these methods fix particles to allow spatial resolution of the particle ensembles. The use of vanillic acid as a possible enhancement to ablation was also studied. A vanillic acid coating of the particles fixed on top of the gelatin substrate was not found to have any positive effect on either signal intensity or precision. The mixing of vanillic acid in the collodion solution used to coat the filter paper increased ablation signal intensity by a factor of 4 to 5. There was little effect on precision, though. The collodion on filter paper method and the gelatin method of resolving particles have shown themselves to be possible tools in fighting proliferation of nuclear weapons and material. Future applications of LA-ICP-MS are only limited by the imagination of the investigator. Any material that can be ablated and aerosolized is a potential material for analysis by LA-ICP-MS. Improvements in aerosol transport, ablation chamber design, and laser focusing can make possible the ablation and analysis of very small amounts of material. This may perhaps lead to more possible uses in forensics. A similar method to the one used in Chapter 3 could perhaps be used to match drug residue to the place of origin. Perhaps a link could be made based on the elements leached from the soil by plants used to make drugs. This may have a specific pattern based on where the plant was grown. Synthetic drugs are produced in clandestine laboratories that are often times very dirty. The dust, debris, and unique materials in the lab environment could create enough variance to perhaps match drugs produced there to samples obtained off the street. Even if the match was not strong enough to be evidence, the knowledge that many sa
Messerly, Joshua D.
High Mass Accuracy and High Mass Resolving Power FT-ICR Secondary...
High Mass Accuracy and High Mass Resolving Power FT-ICR Secondary Ion Mass Spectrometry for Biological Tissue Imaging. High Mass Accuracy and High Mass Resolving Power FT-ICR...
Correlation of rocket propulsion fuel properties with chemical composition using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry followed by partial least squares regression analysis
There is an increased need to more fully assess and control the composition of kerosene based rocket propulsion fuels, namely RP-1 and RP-2. In particular, it is crucial to be able to make better quantitative connections between the following three attributes: (a) fuel performance, (b) fuel properties (flash point, density, kinematic viscosity, net heat of combustion, hydrogen content, etc) and (c) the chemical composition of a given fuel (i.e., specific chemical compounds and compound classes present as a result of feedstock blending and processing). Indeed, recent efforts in predicting fuel performance through modeling put greater emphasis on detailed and accurate fuel properties and fuel compositional information. In this regard, advanced distillation curve (ADC) metrology provides improved data relative to classical boiling point and volatility curve techniques. Using ADC metrology, data obtained from RP-1 and RP-2 fuels provides compositional variation information that is directly relevant to predictive modeling of fuel performance. Often, in such studies, one-dimensional gas chromatography (GC) combined with mass spectrometry (MS) is typically employed to provide chemical composition information. Building on approaches using GC-MS, but to glean substantially more chemical composition information from these complex fuels, we have recently studied the use of comprehensive two dimensional gas chromatography combined with time-of-flight mass spectrometry (GC � GC - TOFMS) to provide chemical composition data that is significantly richer than that provided by GC-MS methods. In this report, by applying multivariate data analysis techniques, referred to as chemometrics, we are able to readily model (correlate) the chemical compositional information from RP-1 and RP-2 fuels provided using GC � GC - TOFMS, to the fuel property information such as that provided by the ADC method and other specification properties. We anticipate that this new chemical analysis strategy will have broad implications for the development of high fidelity composition-property models, leading to an optimized approach to fuel formulation and specification for advanced engine cycles.
Kehimkar, Benjamin; Hoggard, Jamin C.; Marney, Luke C.; Billingsley, Matthew; Fraga, Carlos G.; Bruno, Thomas J.; Synovec, Robert E.
Mexico City Aerosol Analysis During Milagro Using High Resolution Aerosol Mass Spectrometry at the Urban Supersite (T0) - Part 1: Fine Particle Composition and Organic Source Apportionment.
Submicron aerosol was analyzed during the MILAGRO field campaign in March 2006 at the T0 urban supersite in Mexico City with a High-Resolution Aerosol Mass Spectrometer (AMS) and complementary instrumentation. Positive ...
Aiken, A. C.
Molecular Characterization of Organic Aerosols Using Nanospray...
Ionization-Mass Spectrometry. Abstract: Nanospray desorption electrospray ionization (Nano-DESI) combined with high-resolution mass spectrometry (HRMS) is a promising approach...
Mexico City Aerosol Analysis during MILAGRO using High Resolution Aerosol Mass Spectrometry at the Urban Supersite (T0). Part 1: Fine Particle Composition and Organic Source Apportionment
Submicron aerosol was analyzed during the MILAGRO field campaign in March 2006 at the T0 urban supersite in Mexico City with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and complementary instrumentation. Mass concentrations, diurnal cycles, and size distributions of inorganic and organic species are similar to results from the CENICA supersite in April 2003 with organic aerosol (OA) comprising about half of the fine PM mass. Positive Matrix Factorization (PMF) analysis of the high resolution OA spectra identifies three major components: chemically-reduced urban primary emissions (hydrocarbon-like OA, HOA), oxygenated OA (OOA, mostly secondary OA or SOA), and biomass burning OA (BBOA) that correlates with levoglucosan and acetonitrile. BBOA includes several very large plumes from regional fires and likely also some refuse burning.
Aiken, Allison; Salcedo, D.; Cubison, Michael J.; Huffman, J.; DeCarlo, Peter; Ulbrich, Ingrid M.; Docherty, Kenneth S.; Sueper, D. T.; Kimmel, Joel; Worsnop, Douglas R.; Trimborn, Achim; Northway, Megan; Stone, Elizabeth A.; Schauer, James J.; Volkamer, Rainer M.; Fortner, Edward; de Foy, B.; Wang, Jian; Laskin, Alexander; Shutthanandan, V.; Zheng, Junsheng; Zhang, Renyi; Gaffney, Jeffrey S.; Marley, Nancy A.; Paredes-Miranda, Guadalupe L.; Arnott, W. P.; Molina, Luisa T.; Sosa, G.; Jimenez, Jose L.
New constraints on methane fluxes and rates of anaerobic methane oxidation in a Gulf of Mexico brine pool via in situ mass spectrometry
New constraints on methane fluxes and rates of anaerobic methane oxidation in a Gulf of Mexico Keywords: Methane flux Mass spectrometer Brine pool Methane oxidation Gulf of Mexico a b s t r a c t Deep heterogeneity. In particular, biogeochemical fluxes of volatiles such as methane remain largely unconstrained
Girguis, Peter R.
Mexico City aerosol analysis during MILAGRO using high resolution aerosol mass spectrometry at the urban supersite (T0) - Part 1: Fine particle composition and organic source apportionment
Submicron aerosol was analyzed during the MILAGRO field campaign in March 2006 at the T0 urban supersite in Mexico City with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and complementary instrumentation. Mass concentrations, diurnal cycles, and size distributions of inorganic and organic species are similar to results from the CENICA supersite in April 2003 with organic aerosol (OA) comprising about half of the fine PM mass. Positive Matrix Factorization (PMF) analysis of the high resolution OA spectra identified three major components: chemically-reduced urban primary emissions (hydrocarbon-like OA, HOA), oxygenated OA (OOA, mostly secondary OA or SOA), and biomass burning OA (BBOA) that correlates with levoglucosan and acetonitrile. BBOA includes several very large plumes from regional fires and likely also some refuse burning. A fourth OA component is a small local nitrogen-containing reduced OA component (LOA) which accounts for 9% of the OA mass but one third of the organic nitrogen, likely as amines. OOA accounts for almost half of the OA on average, consistent with previous observations. OA apportionment results from PMF-AMS are compared to the PM{sub 2.5} chemical mass balance of organic molecular markers (CMB-OMM, from GC/MS analysis of filters). Results from both methods are overall consistent. Both assign the major components of OA to primary urban, biomass burning/woodsmoke, and secondary sources at similar magnitudes. The 2006 Mexico City emissions inventory underestimates the urban primary PM{sub 2.5} emissions by a factor of {approx}4, and it is {approx}16 times lower than afternoon concentrations when secondary species are included. Additionally, the forest fire contribution is at least an order-of-magnitude larger than in the inventory.
Aiken, A.C.; Wang, J.; Salcedo, D.; Cubison, M. J.; Huffman, J. A.; DeCarlo, P. F.; Ulbrich, I. M.; Docherty, K. S.; Sueper, D.; Kimmel, J. R.; Worsnop, D. R.; Trimborn, A.; Northway, M.; Stone, E. A.; Schauer, J. J.; Volkamer, R. M.; Fortner, E.; de Foy, B.; Laskin, A.; Shutthanandan, V.; Zheng, J.; Zhang, R.; Gaffney, J.; Marley, N. A.; Paredes-Miranda, G.; Arnott, W. P.; Molina, L. T.; Sosa, G.; Jimenez, J. L.
(Ionization in liquids)
This document describes charge transport following ionization of model liquids and how this process may be important in carcinogenesis. 15 refs., 2 figs., 4 tabs. (MHB)
LipidMiner: A Software for Automated Identification and Quantification of Lipids from Multiple Liquid Chromatography-Mass Spectrometry Data Files
We have developed a tool for automated, high-throughput analysis of LC-MS/MS data files, which greatly simplifies LC-MS based lipidomics analysis. Our results showed that LipidMiner is accurate and comprehensive in identification and quantification of lipid molecular species. In addition, the workflow implemented in LipidMiner is not limited to identification and quantification of lipids. If a suitable metabolite library is implemented in the library matching module, LipidMiner could be reconfigured as a tool for general metabolomics data analysis. It is of note that LipidMiner currently is limited to singly charged ions, although it is adequate for the purpose of lipidomics since lipids are rarely multiply charged,[14] even for the polyphosphoinositides. LipidMiner also only processes file formats generated from mass spectrometers from Thermo, i.e. the .RAW format. In the future, we are planning to accommodate file formats generated by mass spectrometers from other predominant instrument vendors to make this tool more universal.
Meng, Da; Zhang, Qibin; Gao, Xiaoli; Wu, Si; Lin, Guang
Quadrupole mass spectrometry and time-of-flight analysis of ions resulting from 532 nm pulsed laser ablation of Ni, Al, and ZnO targets
This work describes the design and validation of an instrument to measure the kinetic energies of ions ejected by the pulsed laser ablation (PLA) of a solid target. Mass spectra show that the PLA of Ni, Al, and ZnO targets, in vacuum, using the second harmonic of a Nd:YAG laser (532 nm, pulse duration {approx}10 ns) generates abundant X{sup n+} ions (n{<=}3 for Ni, {<=}2 for Al, {<=}3 and {<=}2 for Zn and O respectively from ZnO). Ions are selected by their mass/charge (m/z) ratio prior to the determination of their times of flight. PLA of Ni has been studied in most detail. The mean velocities of ablated Ni{sup n+} ions are shown to follow the trend v(Ni{sup 3+})>v(Ni{sup 2+})>v(Ni{sup +}). Data from Ni{sup 2+} and Ni{sup 3+} are fitted to shifted Maxwellian functions and agree well with a model which assumes both thermal and Coulombic contributions to ion velocities. The dependence of ion velocities on laser pulse energy (and fluence) is investigated, and the high energy data are shown to be consistent with an effective accelerating voltage of {approx}90 V within the plume. The distribution of velocities associated with Ni{sup 3+} indicates a population at cooler temperature than Ni{sup 2+}.
Sage, Rebecca S.; Cappel, Ute B.; Ashfold, Michael N. R.; Walker, Nicholas R. [School of Chemistry, University of Bristol, Bristol BS8 1TS (United Kingdom)
Accurate determination of Curium and Californium isotopic ratios by inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) in 248Cm samples for transmutation studies
The French Atomic Energy Commission has carried out several experiments including the mini-INCA (INcineration of Actinides) project for the study of minor-actinide transmutation processes in high intensity thermal neutron fluxes, in view of proposing solutions to reduce the radiotoxicity of long-lived nuclear wastes. In this context, a Cm sample enriched in {sup 248}Cm ({approx}97 %) was irradiated in thermal neutron flux at the High Flux Reactor (HFR) of the Laue-Langevin Institute (ILL). This work describes a quadrupole ICP-MS (ICP-QMS) analytical procedure for precise and accurate isotopic composition determination of Cm before sample irradiation and of Cm and Cf after sample irradiation. The factors that affect the accuracy and reproducibility of isotopic ratio measurements by ICP-QMS, such as peak centre correction, detector dead time, mass bias, abundance sensitivity and hydrides formation, instrumental background, and memory blank were carefully evaluated and corrected. Uncertainties of the isotopic ratios, taking into account internal precision of isotope ratio measurements, peak tailing, and hydrides formations ranged from 0.3% to 1.3%. This uncertainties range is quite acceptable for the nuclear data to be used in transmutation studies.
Gourgiotis, A.; Isnard, H.; Aubert, M.; Dupont, E.; AlMahamid, I.; Cassette, P.; Panebianco, S.; Letourneau, A.; Chartier, F.; Tian, G.; Rao, L.; Lukens, W.
Nuclear Masses in Astrophysics
Among all nuclear ground-state properties, atomic masses are highly specific for each particular combination of N and Z and the data obtained apply to a variety of physics topics. One of the most crucial questions to be addressed in mass spectrometry of unstable radionuclides is the one of understanding the processes of element formation in the Universe. To this end, accurate atomic mass values of a large number of exotic nuclei participating in nucleosynthesis are among the key input data in large-scale reaction network calculations. In this paper, a review on the latest achievements in mass spectrometry for nuclear astrophysics is given.
Christine Weber; Klaus Blaum; Hendrik Schatz
Ultra High Mass Range Mass Spectrometer System
Applicant's present invention comprises mass spectrometer systems that operate in a mass range from 1 to 10.sup.16 DA. The mass spectrometer system comprising an inlet system comprising an aerodynamic lens system, a reverse jet being a gas flux generated in an annulus moving in a reverse direction and a multipole ion guide; a digital ion trap; and a thermal vaporization/ionization detector system. Applicant's present invention further comprises a quadrupole mass spectrometer system comprising an inlet system having a quadrupole mass filter and a thermal vaporization/ionization detector system. Applicant's present invention further comprises an inlet system for use with a mass spectrometer system, a method for slowing energetic particles using an inlet system. Applicant's present invention also comprises a detector device and a method for detecting high mass charged particles.
Reilly, Peter T. A. [Knoxville, TN
A surface ionization source
The main part of the work described herein is the development and testing of a surface ionization source for use on a collinear fast beam laser spectroscopy apparatus. A description of the previously existing fast beam apparatus is given...
Buzatu, Daniel J.
ablation-absorption ratio spectrometry: Topics by E-print Network
isotopes 2 A gas chromatographypyrolysisisotope ratio mass spectrometry system for high-precision dD measurements Environmental Sciences and Ecology Websites Summary: of...
Ionized Hydrogen at Large Galactocentric Distances
We summarize recent attempts to detect warm ionized gas at large galactocentric distances. This includes searching for gas at the edges of spirals, in between cluster galaxies, towards extragalactic HI clouds, and towards high velocity clouds and the Magellanic Stream in the Galaxy. With the exception of extragalactic HI clouds, all of these experiments have proved successful. Within each class, we have only observed a handful of objects. It is premature to assess what fraction of the missing baryonic mass fraction might be in the form of ionized gas. But, in most cases, the detections provide a useful constraint on the ambient ionizing flux, and in the case of spiral edges, can even trace dark matter haloes out to radii beyond the reach of radio telescopes.
J. Bland-Hawthorn
High-Compression-Ratio; Atkinson-Cycle Engine Using Low-Pressure Direct Injection and Pneumatic-Electronic Valve Actuation Enabled by Ionization Current and Foward-Backward Mass Air Flow Sensor Feedback
This report describes the work completed over a two and one half year effort sponsored by the US Department of Energy. The goal was to demonstrate the technology needed to produce a highly efficient engine enabled by several technologies which were to be developed in the course of the work. The technologies included: (1) A low-pressure direct injection system; (2) A mass air flow sensor which would measure the net airflow into the engine on a per cycle basis; (3) A feedback control system enabled by measuring ionization current signals from the spark plug gap; and (4) An infinitely variable cam actuation system based on a pneumatic-hydraulic valve actuation These developments were supplemented by the use of advanced large eddy simulations as well as evaluations of fuel air mixing using the KIVA and WAVE models. The simulations were accompanied by experimental verification when possible. In this effort a solid base has been established for continued development of the advanced engine concepts originally proposed. Due to problems with the valve actuation system a complete demonstration of the engine concept originally proposed was not possible. Some of the highlights that were accomplished during this effort are: (1) A forward-backward mass air flow sensor has been developed and a patent application for the device has been submitted. We are optimistic that this technology will have a particular application in variable valve timing direct injection systems for IC engines. (2) The biggest effort on this project has involved the development of the pneumatic-hydraulic valve actuation system. This system was originally purchased from Cargine, a Swedish supplier and is in the development stage. To date we have not been able to use the actuators to control the exhaust valves, although the actuators have been successfully employed to control the intake valves. The reason for this is the additional complication associated with variable back pressure on the exhaust valves when they are opened. As a result of this effort, we have devised a new design and have filed for a patent on a method of control which is believed to overcome this problem. The engine we have been working with originally had a single camshaft which controlled both the intake and exhaust valves. Single cycle lift and timing control was demonstrated with this system. (3) Large eddy simulations and KIVA based simulations were used in conjunction with flow visualizations in an optical engine to study fuel air mixing. During this effort we have devised a metric for quantifying fuel distribution and it is described in several of our papers. (4) A control system has been developed to enable us to test the benefits of the various technologies. This system used is based on Opal-RT hardware and is being used in a current DOE sponsored program.
Harold Schock; Farhad Jaberi; Ahmed Naguib; Guoming Zhu; David Hung
A VUV photoionization measurement and ab-initio calculation of the ionization energy of gas phase SiO2
In this work we report on the detection and vacuum-ultraviolet (VUV) photoionization of gas phase SiO2 generated in situ via laser ablation of silicon in a CO2 molecular beam. The resulting species are investigated by single photon ionization with tunable VUV synchrotron radiation and mass analyzed using reflectron mass spectrometry. Photoionization efficiency (PIE) curves are recorded for SiO and SiO2 and ionization energy estimates are revealed from such measurements. A state-to-state ionizationenergy of 12.60 (+-0.05) eV is recorded by fitting two prominent peaks in the PIE curve for the following process: 1SUM O-Si-O --> 2PRODg [O-Si-O]+. Electronic structure calculations aid in the interpretation of the photoionization process and allow for identification of the symmetric stretch of 2PRODg [O-Si-O]+ which is observed in the PIE spectrum to be 0.11 eV (890 cm-1) above the ground state of the cation and agrees with the 892 cm-1 symmetric stretch frequency calculated at the CCSD(T)/aug-cc-pVTZ level.
Kostko, Oleg; Ahmed, Musahid; Metz, Ricardo B.
Mass spectrometry with a very small cyclotron
It is proposed that direct detection of natural radioisotopes can be accomplished by using a very low energy (20 to 100 keV) cyclotron accelerating negative ions.
Muller, R.A.; Tans, P.P.; Mast, T.S.; Welch, J.J.
Mapping Molecular Space with Mass Spectrometry /
L & Owende P (2010) Biofuels from microalgae�A review of2009) Microalgae as a raw material for biofuels production.microalgae. Current research aims to produce traditional biofuels
Nguyen, Don Duy
Signatures for Mass Spectrometry Data Quality
Ensuring data quality and proper instrument functionality is a prerequisite for scientific investigation. Manual validation for quality assurance is time consuming, expensive and subjective. Metrics for describing various features of LC-MS data have been developed to assist operators in discriminating poor (out of control) and good (in control) datasets. However, the wide variety of instrument specifications and LC-MS configurations precludes applying a simple range of acceptable values or cutoffs for such metrics. We explored a variety of statistical modeling approaches to predict the quality of LC-MS data. Using 1164 manually classified quality control (QC) LC-MS datasets, we fit logistic regression classification models to the QC data to predict whether a dataset is in or out of control. Model parameters were optimized by minimizing a loss function that accounts for the tradeoff between false positive and false negative errors. The optimal logistic regression classifier models detected bad data sets with high sensitivity (i.e. low false negative rate) while maintaining high specificity (i.e. controlling the false positive rate). As an example, predictions for Velos-Orbitrap instrumentation data had a sensitivity of 93.7% in detecting out of control datasets with a false positive rate of 8.3%. In comparison, we investigated the performance of several single metrics in predicting dataset quality. While maintaining a sensitivity of 93.7%, the corresponding false positive rates for these single-metric models unacceptably ranged from 32% to 97.7%. Finally, we evaluated the performance of the
Amidan, Brett G.; Orton, Daniel J.; Lamarche, Brian L.; Monroe, Matthew E.; Moore, Ronald J.; Venzin, Alexander M.; Smith, Richard D.; Sego, Landon H.; Tardiff, Mark F.; Payne, Samuel H.
microalgae. Current research aims to produce traditional biofuels from algae, but their potential to generate sustainable energy
for sev eral cluster sou rce nozzle condition s. Heliu m gas pressu re at the tim e of v aporization of solid m aterial played the key role in cluster size range obtain ed. Th e effect of pressu re was thorou
Maruyama, Shigeo
Aerosol mass spectrometry systems and methods
A system according to one embodiment includes a particle accelerator that directs a succession of polydisperse aerosol particles along a predetermined particle path; multiple tracking lasers for generating beams of light across the particle path; an optical detector positioned adjacent the particle path for detecting impingement of the beams of light on individual particles; a desorption laser for generating a beam of desorbing light across the particle path about coaxial with a beam of light produced by one of the tracking lasers; and a controller, responsive to detection of a signal produced by the optical detector, that controls the desorption laser to generate the beam of desorbing light. Additional systems and methods are also disclosed.
Fergenson, David P.; Gard, Eric E.
L & Oliveira AC (2009) Microalgae as a raw material forP (2010) Biofuels from microalgae�A review of technologiesThe tide turns towards microalgae. Current research aims to
Next-Generation Mass Spectrometry | EMSL
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CAMS Center for Accelerator Mass Spectrometry
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Application of Electron Transfer Dissociation Mass Spectrometry...
glycation of peptides and proteins by D-glucose has important implications in diabetes mellitus research, particularly in the context of development of diabetic...
Beyond single particle mass spectrometry: multidimensional characterisation
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Electrospray Mass Spectrometry | The Ames Laboratory
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Signatures for Mass Spectrometry Data Quality. | EMSL
AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE:1 First Use of Energy for All Purposes (Fuel and Nonfuel),Feet) Year Jan Feb Mar Apr MayAtmosphericNuclear Security Administrationcontroller systemsBi (2)Sharing Smart GridShift EndSidney D.Christopher
Gas-Phase Synthesis of Singly and Multiply Charged Polyoxovanadate Anions Employing Electrospray Ionization and Collision Induced Dissociation
Electrospray ionization mass spectrometry (ESI-MS) combined with in-source fragmentation and tandem mass spectrometry (MS/MS) experiments were used to generate a wide range of multiply charged vanadium oxide cluster anions including VxOyn- and VxOyCln- ions (x = 1 ? 14, y= 2 ? 36, n = 1 ? 3), protonated clusters, and ligand-bound VxOyn- species. These cluster anions were produced by electrospraying a solution of tetradecavanadate, V14O36Cl(L)5 (L= Et4N+, tetraethylammonium), in acetonitrile. Under mild source conditions, ESI-MS generates a distribution of doubly and triply charged VxOyCln- and VxOyCl(L)(n-1)- clusters predominantly containing 14 vanadium atoms. Accurate mass measurement using high-resolution mass spectrometry (m/?m = 60,000 at m/z 410) enabled unambiguous assignment of the elemental composition of the majority of peaks in the ESI-MS spectrum. In addition, high-sensitivity mass spectrometry allowed the charge state of the cluster ions to be assigned based on the separation of the major from the minor isotope of vanadium. In-source fragmentation resulted in facile formation of smaller VxOyCl(1-2)- and VxOy(1-2)- anions. Collision-induced dissociation (CID) experiments enabled systematic study of the gas-phase fragmentation pathways of the cluster anions generated from solution. Surprisingly simple fragmentation patterns were obtained for all singly and doubly charged VxOyCl and VxOy species generated through multiple MS/MS experiments. In contrast, cluster ions originating directly from solution produced comparatively complex CID spectra. These results indicate that low-energy CID results in formation of stable cage-like structures of VxOyCl and VxOy anions. Furthermore, solution-phase synthesis of one precursor cluster combined with gas-phase CID is an efficient approach for the top-down synthesis of a wide range of multiply charged gas-phase metal oxide clusters for subsequent investigations of structure and reactivity.
Al Hasan, Naila M.; Johnson, Grant E.; Laskin, Julia
Charge Retention by Gold Clusters on Surfaces Prepared Using Soft Landing of Mass Selected Ions
Monodisperse gold clusters have been prepared on surfaces in different charge states through soft landing of mass-selected ions. Ligand-stabilized gold clusters were prepared in methanol solution by reduction of chloro(triphenylphosphine)gold(I) with borane tert-butylamine complex in the presence of 1,3-bis(diphenylphosphino)propane. Electrospray ionization was used to introduce the clusters into the gas-phase and mass-selection was employed to isolate a single ionic cluster species (Au11L53+, L = 1,3-bis(diphenylphosphino)propane) which was delivered to surfaces at well controlled kinetic energies. Using in-situ time of flight secondary ion mass spectrometry (TOF-SIMS) it is demonstrated that the Au11L53+ cluster retains its 3+ charge state when soft landed onto the surface of a 1H,1H,2H,2H-
Johnson, Grant E.; Priest, Thomas A.; Laskin, Julia
High Resolution Ion Mobility Spectrometry with Increased Ion Transmission: Exploring the Analytical Utility of Periodic-Focusing DC Ion Guide Drift Cells
Drift tube ion mobility spectrometry (IMS) is a powerful, post-ionization separation that yields structural information of ions through an ion-neutral collision cross section. The ion-neutral collision cross section is governed by the collision...
Blase, Ryan Christopher
Hysteresis of ionization waves
A quasi-logistic, nonlinear model for ionization wave modes is introduced. Modes are due to finite size of the discharge and current feedback. The model consists of competing coupled modes and it incorporates spatial wave amplitude saturation. The hysteresis of wave mode transitions under current variation is reproduced. Sidebands are predicted by the model and found in experimental data. The ad hoc model is equivalent to a general--so-called universal--approach from bifurcation theory.
Dinklage, A. [Max-Planck-Institut fuer Plasmaphysik, EURATOM-Association, Wendelsteinstr. 1, 17491 Greifswald (Germany); Bruhn, B.; Testrich, H. [Institut fuer Physik, E.-M.-Arndt Universitaet Greifswald, Felix-Hausdorff-Str. 6, 17487 Greifswald (Germany); Wilke, C. [Leibniz-Institut fuer Plasmaforschung und Technologie, Felix-Hausdorff-Str. 2, 17489 Greifswald (Germany)
Spatially-Resolved Analysis of Glycolipids and Metabolites in Living Synechococcus sp. PCC7002 Using Nanospray Desorption Electrospray Ionization
Microorganisms release a diversity of organic compounds that couple interspecies metabolism, enable communication, or provide benefits to other microbes. Increased knowledge of microbial metabolite production will contribute to understanding of the dynamic microbial world and can potentially lead to new developments in drug discovery, biofuel production, and clinical research. Nanospray desorption electrospray ionization (nano-DESI) is an ambient ionization technique that enables detailed chemical characterization of molecules from a specific location on a surface without special sample pretreatment. Due to its ambient nature, living bacterial colonies growing on agar plates can be rapidly and non-destructively analyzed. We performed spatially resolved nano-DESI analysis of living Synechococcus sp. PCC 7002 colonies on agar plates. We use high resolution mass spectrometry and MS/MS analysis of the living Synechococcus sp. PCC 7002 colonies to detect metabolites and lipids, and confirm their identities. We found that despite the high salt content of the agar (osmolarity ca. 700 mM), nano-DESI analysis enables detailed characterization of metabolites produced by the colony. Using this technique, we identified several glycolipids found on the living colonies and examined the effect of the age of the colony on the chemical gradient of glucosylglycerol secreted onto agar.
Lanekoff, Ingela T.; Geydebrekht, Oleg V.; Pinchuk, Grigoriy E.; Konopka, Allan; Laskin, Julia
The multiphoton ionization of uranium hexafluoride
Multiphoton ionization (MPI) time-of-flight mass spectroscopy and photoelectron spectroscopy studies of UF{sub 6} have been conducted using focused light from the Nd:YAG laser fundamental ({lambda}=1064 nm) and its harmonics ({lambda}=532, 355, or 266 nm), as well as other wavelengths provided by a tunable dye laser. The MPI mass spectra are dominated by the singly and multiply charged uranium ions rather than by the UF{sub x}{sup +} fragment ions even at the lowest laser power densities at which signal could be detected. The laser power dependence of U{sup n+} ions signals indicates that saturation can occur for many of the steps required for their ionization. In general, the doubly-charged uranium ion (U{sup 2+}) intensity is much greater than that of the singly-charged uranium ion (U{sup +}). For the case of the tunable dye laser experiments, the U{sup n+} (n = 1- 4) wavelength dependence is relatively unstructured and does not show observable resonance enhancement at known atomic uranium excitation wavelengths. The dominance of the U{sup 2+} ion and the absence or very small intensities of UF{sub x}{sup +} fragments, along with the unsaturated wavelength dependence, indicate that mechanisms may exist other than ionization of bare U atoms after the stepwise photodissociation of F atoms from the parent molecule.
Armstrong, D.P. (Oak Ridge K-25 Site, TN (United States). UEO Enrichment Technical Operations Div.)
Modulated voltage metastable ionization detector
Metastable ionization detectors used for chromatographic analysis usually employa fixed high voltage for the ionization potential. For this reason, the operating range is limited to about three orders of magnitude. By use of the technique disclosed in the instant invention, operating ranges of about nine orders of magnitude are obtained. The output current from a metastable ionization detector (MID) is applied to a modulation voltage circuit. An adjustment is made to balance out the background current, and an output current, above background, is applied to an input of a strip chart recorder. For low level concentrations, i.e., low detected output current, the ionization potential will be at a maximum and the metastable ionization detector will operate at its most sensitive level. When the detected current from the metastable ionization detector increases above a predetermined threshold level, a voltage control circuit is activated which turns on a high voltage transistor which acts to reduce the ionization potential. The ionization potential applied to the metastable ionization detector is then varied so as to maintain the detected signal level constant. The variation in ionization potential is now related to the concentration fo the constituent and a representative amplitude is applied to another input of said strip chart recorder.
Carle, G. C.; Humphry, D. E.; Kojiro, D. R.
Chemical Analysis of Complex Organic Mixtures Using Reactive...
Mass Spectrometry. Abstract: Reactive nanospray desorption electrospray ionization (nano-DESI) combined with high-resolution mass spectrometry was utilized for the analysis of...
Plasma Production via Field Ionization
Plasma production via field ionization occurs when an incoming particle beam is sufficiently dense that the electric field associated with the beam ionizes a neutral vapor or gas. Experiments conducted at the Stanford Linear Accelerator Center explore the threshold conditions necessary to induce field ionization by an electron beam in a neutral lithium vapor. By independently varying the transverse beam size, number of electrons per bunch or bunch length, the radial component of the electric field is controlled to be above or below the threshold for field ionization. Additional experiments ionized neutral xenon and neutral nitric oxide by varying the incoming beam's bunch length. A self-ionized plasma is an essential step for the viability of plasma-based accelerators for future high-energy experiments.
O'Connell, C.L.; Barnes, C.D.; Decker, F.; Hogan, M.J.; Iverson, R.; Krejcik, P.; Siemann, R.; Walz, D.R.; /SLAC; Clayton, C.E.; Huang, C.; Johnson, D.K.; Joshi, C.; Lu,; Marsh, K.A.; Mori, W.; Zhou, M.; /UCLA; Deng, S.; Katsouleas, T.; Muggli, P.; Oz, E.; /Southern California U.
Investigation of high temperature gaseous species by Knudsen cell mass spectrometry above the condensed systems Cu-Y-Ru-C, Ag-Y-Ru-C, and Au-Y- Ru-C
of the total ion intensities listed in Tables 2 through 5, + + except those for RuC and YC2, were calculated by dividing the individual isotopic species by the isotopic abundance of that species according to Equation 1, where I is the total intensity of all... not be used because their mass to charge ratios overlap. For these iona, an + algebraic equation was used which compared the ratios of YC (Mass 113), YC2 (Mass 114), RuC (Mass 113), and RuC (Mass 114). The + + + calculated isotopic abundances...
Wilhite, Dale Wayne
aerosol mass spectrometer: Topics by E-print Network
2004. The concentration of a species Zhang, Qi 8 Development of a thermal desorption chemical ionization mobility mass spectrometer for the speciation of ultrafine aerosols. Open...
I. IONIZATION COOLING A. Introduction
ionization cooling techniques to reduce the 6�dimensional phase space emittance. B. Cooling TheoryI. IONIZATION COOLING A. Introduction The muon beam at the end of the decay channel is very intense for beam cooling. Cooling by synchrotron radiation, conventional stochastic cooling and conventional
McDonald, Kirk
Ionizing radiation detector
An ionizing radiation detector is provided which is based on the principle of analog electronic integration of radiation sensor currents in the sub-pico to nano ampere range between fixed voltage switching thresholds with automatic voltage reversal each time the appropriate threshold is reached. The thresholds are provided by a first NAND gate Schmitt trigger which is coupled with a second NAND gate Schmitt trigger operating in an alternate switching state from the first gate to turn either a visible or audible indicating device on and off in response to the gate switching rate which is indicative of the level of radiation being sensed. The detector can be configured as a small, personal radiation dosimeter which is simple to operate and responsive over a dynamic range of at least 0.01 to 1000 R/hr.
Thacker, Louis H. (Knoxville, TN)
High resolution FT-ICR mass spectral analysis of bio-oil and residual water soluble organics produced by hydrothermal liquefaction of the marine microalga Nannochloropsis salina
We report a detailed compositional characterization of a bio-crude oil and aqueous by-product from hydrothermal liquefaction of Nannochloropsis salina by direct infusion Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) in both positive- and negative-ionization modes. The FT-ICR MS instrumentation approach facilitates direct assignment of elemental composition to >7000 resolved mass spectral peaks and three-dimensional mass spectral images for individual heteroatom classes highlight compositional diversity of the two samples and provide a baseline description of these materials. Aromatic nitrogen compounds and free fatty acids are predominant species observed in both the bio-oil and aqueous fraction. Residual organic compounds present in the aqueous fraction show distributions that are slightly lower in both molecular ring and/or double bond value and carbon number relative to those found in the bio-oil, albeit with a high degree of commonality between the two compositions.
Sudasinghe, Nilusha; Dungan, Barry; Lammers, Peter; Albrecht, Karl O.; Elliott, Douglas C.; Hallen, Richard T.; Schaub, Tanner
Optical ionization detector
An optical ionization detector wherein a beam of light is split so that one arm passes through a fiber optics and the other arm passes through a gas-filled region, and uses interferometry to detect density changes in a gas when charged particles pass through it. The gas-filled region of the detector is subjected to a high electric field and as a charged particle traverses this gas region electrons are freed from the cathode and accelerated so as to generate an electron avalanche which is collected on the anode. The gas density is effected by the electron avalanche formation and if the index or refraction is proportional to the gas density the index will change accordingly. The detector uses this index change by modulating the one arm of the split light beam passing through the gas, with respect to the other arm that is passed through the fiber optic. Upon recombining of the beams, interference fringe changes as a function of the index change indicates the passage of charged particles through the gaseous medium. 3 figures.
Wuest, C.R.; Lowry, M.E.
An optical ionization detector wherein a beam of light is split so that one arm passes through a fiber optics and the other arm passes through a gas-filled region, and uses interferometry to detect density changes in a gas when charged particles pass through it. The gas-filled region of the detector is subjected to a high electric field and as a charged particle traverses this gas region electrons are freed from the cathode and accelerated so as to generate an electron avalanche which is collected on the anode. The gas density is effected by the electron avalanche formation and if the index or refraction is proportional to the gas density the index will change accordingly. The detector uses this index change by modulating the one arm of the split light beam passing through the gas, with respect to the other arm that is passed through the fiber optic. Upon recombining of the beams, interference fringe changes as a function of the index change indicates the passage of charged particles through the gaseous medium.
Wuest, Craig R. (Danville, CA); Lowry, Mark E. (Castro Valley, CA)
Vacuum-Ultraviolet Photoionization and Mass Spectrometric Characterization of Lignin Monomers Coniferyl and Sinapyl Alcohols
The fragmentation mechanisms of monolignols under various energetic processes are studied with jet-cooled thermal desorption molecular beam (TDMB) mass spectrometry (MS), 25 keV Bi3+ secondary ion MS (SIMS), synchrotron vacuum-ultraviolet secondary neutral MS (VUV-SNMS) and theoretical methods. Experimental and calculated appearance energies of fragments observed in TDMB MS indicate that the coniferyl alcohol photoionization mass spectra contain the molecular parent and several dissociative photoionization products. Similar results obtained for sinapyl alcohol are also discussed briefly. Ionization energies of 7.60 eV ? 0.05 eV for coniferyl alcohol and<7.4 eV for both sinapyl and dihydrosinapyl alcohols are determined. The positive ion SIMS spectrum of coniferyl alcohol shares few characteristic peaks (m/z = 137 and 151) with the TDMB mass spectra, shows extensive fragmentation, and does not exhibit clear molecular parent signals. VUV-SNMS spectra, on the other hand, are dominated by the parent ion and main fragments also present in the TDMB spectra. Molecular fragmentation in VUV-SNMS spectra can be reduced by increasing the extraction delay time. Some features resembling the SIMS spectra are also observed in the desorbed neutral products. The monolignol VUV-SNMS peaks shared with the TDMB mass spectra suggest that dissociative photoionization of ion-sputtered neutral molecules predominate in the VUV-SNMS mass spectra, despite the extra internal energy imparted in the initial ion impact. The potential applications of these results to imaging mass spectrometry of bio-molecules are discussed.
Takahashi, Lynelle K.; Zhou, Jia; Kostko, Oleg; Golan, Amir; Leone, Stephen R.; Ahmed, Musahid
JOURNAL DE PHYSIQUE Colloque C 2, supplkment au no 3-4, Tome 28, mars-avril1967, page C 2 -87 RAPID SCANNING FOURIER TRANSFORM SPECTROMETRY
scanning serves to mitigate the problems of scintillation and dynamic range for Fourier spectrometry. Scintillation noise due to atmospheric turbulence can easily relegate astronomical spectrometry to the last RAPID SCANNING FOURIER TRANSFORM SPECTROMETRY Block Associates, Inc., Cambridge, Mass., U. S. A. Rksumk
Paris-Sud XI, Universit� de
Field ionization from carbon nanofibers
The Micro Gas Analyzer project aims to develop power-efficient, high resolution, high sensitivity, portable and real-time gas sensors. We developed a field ionizer array based on gated CNTs. Arrays of CNTs are used because ...
Adeoti, Bosun J
Ionizing Radiation Injury (South Carolina)
Broader source: Energy.gov [DOE]
This legislation applies to employers that have more than one employee who engages in activities which involve the presence of ionizing radiation. Employers with less than three employees can...
Resonance ionization for analytical spectroscopy
This invention relates to a method for the sensitive and selective analysis of an atomic or molecular component of a gas. According to this method, the desired neutral component is ionized by one or more resonance photon absorptions, and the resultant ions are measured in a sensitive counter. Numerous energy pathways are described for accomplishing the ionization including the use of one or two tunable pulsed dye lasers.
Hurst, George S. (Oak Ridge, TN); Payne, Marvin G. (Harriman, TN); Wagner, Edward B. (Burchfield Heights, TN)
Linear electric field time-of-flight ion mass spectrometer
A linear electric field ion mass spectrometer having an evacuated enclosure with means for generating a linear electric field located in the evacuated enclosure and means for injecting a sample material into the linear electric field. A source of pulsed ionizing radiation injects ionizing radiation into the linear electric field to ionize atoms or molecules of the sample material, and timing means determine the time elapsed between ionization of atoms or molecules and arrival of an ion out of the ionized atoms or molecules at a predetermined position.
Funsten, Herbert O. (Los Alamos, NM); Feldman, William C. (Los Alamos, NM)
Continuous time-of-flight ion mass spectrometer
A continuous time-of-flight mass spectrometer having an evacuated enclosure with means for generating an electric field located in the evacuated enclosure and means for injecting a sample material into the electric field. A source of continuous ionizing radiation injects ionizing radiation into the electric field to ionize atoms or molecules of the sample material, and timing means determine the time elapsed between arrival of a secondary electron out of said ionized atoms or molecules at a first predetermined location and arrival of a sample ion out of said ionized atoms or molecules at a second predetermined location.
Funsten, Herbert O.; Feldman, William C.
Radiative feedback from ionized gas
H2 formation in metal-free gas occurs via the intermediate H- or H2+ ions. Destruction of these ions by photodissociation therefore serves to suppress H2 formation. In this paper, I highlight the fact that several processes that occur in ionized primordial gas produce photons energetic enough to photodissociate H- or H2+ and outline how to compute the photodissociation rates produced by a particular distribution of ionized gas. I also show that there are circumstances of interest, such as during the growth of HII regions around the first stars, in which this previously overlooked form of radiative feedback is of considerable importance.
S. C. O. Glover
Spectral networks algorithms for de novo interpretation of tandem mass spectra
high-energy collision-induced dissociation spectra of singly protonated peptides by �SeqMS�, a software aid for de novo sequencing by tandem mass spectrometry.
Bandeira, Nuno Filipe Cabrita
andliquid chromatography-tandem mass: Topics by E-print Network
using isotope dilution high performance liquid chromatography-tandem mass spectrometry. Open Access Theses and Dissertations Summary: ??A method has been developed for...
aerosol time-of-flight mass: Topics by E-print Network
Theses and Dissertations Summary: ??The construction of a liquid nitrogen-cooled ion mobility spectrometer coupled with time-of-flight mass spectrometry was implemented to...
Scientific innovation and resonance ionization spectroscopy
An account is presented of the development and appliations of resonance ionization spectroscopy and one atom detection.
Richmond, C.R.
Mass spectrometric characterization of sequence-specific complexes of DNA and transcription factor PU.1 DNA binding domain
Electrospray ionization mass spectrometry (ESI-MS) has been used to study the noncovalent interaction of the 13.5-kDa DNA binding domain of PU.1 (PU.1-DBD) with specific double-stranded DNA (dsDNA) target molecules. Mixtures of PU.1-DBD protein and wildtype target DNA sequence yielded ESI-MS spectra showing only protein-dsDNA complex ions of 1:1 stoichiometry and free dsDNA. When PU.1-DBD protein, wild type target DNA, and a mutant target DNA lacking the consensus sequence were mixed, only the 1:1 complex with the wild-type DNA was observed, consistent with gel electrophoresis mobility shift assay results, demonstrating the observation of sequence-specific protein-dsDNA complexes using ESI-MS. 22 refs., 5 figs., 1 tab.
Cheng, Xueheng; Harms, A.C.; Bruce, J.E. [Pacific Northwest National Lab., Richland, WA (United States)] [and others] [Pacific Northwest National Lab., Richland, WA (United States); and others
Development and evaluation of high resolution quadrupole mass analyzer and an inductively coupled plasma-Mach disk
By definition a plasma is an electrically conducting gaseous mixture containing a significant concentration of cations and electrons. The Inductively Coupled Plasma (ICP) is an electrodeless discharge in a gas at atmospheric pressure. This discharge is an excellent one for vaporizing, atomizing, and ionizing elements. The early development of the ICP began in 1942 by Babat and then by Reed in the early 1960s. This was then followed by the pioneering work of Fassel and coworkers in the late 1960s. Commercial ICP spectrometers were introduced in the mid 1970s. A major breakthrough in the area of ICP took place in the early 1980s when the ICP was shown to be an excellent ion source for mass spectrometry.
Amad, Ma'an Hazem
Mexico City Aerosol Analysis during MILAGRO using High Resolution Aerosol Mass Spectrometry at the Urban Supersite (T0). Part 2: Analysis of the Biomass Burning Contribution and the Modern Carbon Fraction
Submicron aerosol was analyzed during the MILAGRO field campaign in March 2006 at the T0 urban supersite in Mexico City with a High-Resolution Aerosol Mass Spectrometer (AMS) and complementary instrumentation. Positive Matrix Factorization (PMF) of high resolution AMS spectra identified a biomass burning OA (BBOA) component, which includes several large plumes that appear to be from forest fires within the region. Here, we show that the AMS BBOA concentration at T0 correlates with fire counts in the vicinity of Mexico City and that most of the BBOA variability is captured when the FLEXPART model is used for the dispersion of fire emissions as estimated from satellite fire counts. The resulting FLEXPART fire impact index correlates well with the observed BBOA, CH3CN, levoglucosan, and potassium, indicating that wildfires in the region surrounding Mexico City are the dominant source of BBOA at T0 during MILAGRO. The impact of distant BB sources such as the Yucatan is very small during this period. All fire tracers are correlated, with BBOA and levoglucosan showing little background, acetonitrile having a well-known tropospheric background of ~100-150 ppt, and PM2.5 potassium having a background of ~160 ng m-3 (two-thirds of its average concentration), which does not appear to be related to BB sources.
Aiken, Allison; de Foy, B.; Wiedinmyer, Christine; DeCarlo, Peter; Ulbrich, Ingrid M.; Wehrli, M. N.; Szidat, S.; Prevot, A. S. H.; Noda, J.; Wacker, L.; Volkamer, Rainer M.; Fortner, Edward; Wang, J. X.; Laskin, Alexander; Shutthanandan, V.; Zheng, J.; Zhang, Renyi; Paredes-Miranda, Guadalupe L.; Arnott, W. P.; Molina, Luis; Sosa, G.; Querol, X.; Jimenez, J. L.
Biases in Ion Transmission Through an Electrospray Ionization-Mass
AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE:1 First Use of Energy for All Purposes (Fuel and Nonfuel),Feet) Year Jan Feb Mar Apr May JunDatastreamsmmcrcalgovInstrumentsruc DocumentationP-Series to someone6 M. Babzien, I.Program Information
Tissue Imaging Using Nanospray Desorption Electrospray Ionization Mass
AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE:1 First Use of Energy for All Purposes (Fuel and Nonfuel),Feet) Year Jan Feb Mar Apr MayAtmosphericNuclear SecurityTensile Strain Switched Ferromagnetism in Layered NbS2 andThe1A:decisional. 1 B O N N ESpectrometry. |
The Siemens Advanced Quantra Fourier Transform Ion Cyclotron Resonance (FTICR) mass spectrometer was evaluated as an alternative instrument to large double focusing mass spectrometers for gas analysis. High resolution mass spectrometers capable of resolving the common mass isomers of the hydrogen isotopes are used to provide data for accurate loading of reservoirs and to monitor separation of tritium, deuterium, and helium. Conventional double focusing magnetic sector instruments have a resolution that is limited to about 5000. The Siemens FTICR instrument achieves resolution beyond 400,000 and could possibly resolve the tritium ion from the helium-3 ion, which differ by the weight of an electron, 0.00549 amu. Working with Y-12 and LANL, SRNL requested Siemens to modify their commercial Quantra system for low mass analysis. To achieve the required performance, Siemens had to increase the available waveform operating frequency from 5 MHz to 40 MHz and completely redesign the control electronics and software. However, they were able to use the previous ion trap, magnet, passive pump, and piezo-electric pulsed inlet valve design. NNSA invested $1M in this project and acquired four systems, two for Y-12 and one each for SRNL and LANL. Siemens claimed a $10M investment in the Quantra systems. The new Siemens Advanced Quantra demonstrated phenomenal resolution in the low mass range. Resolution greater than 400,000 was achieved for mass 2. The new spectrometer had a useful working mass range to 500 Daltons. However, experiments found that a continuous single scan from low mass to high was not possible. Two useful working ranges were established covering masses 1 to 6 and masses 12 to 500 for our studies. A compromise performance condition enabled masses 1 to 45 to be surveyed. The instrument was found to have a dynamic range of about three orders of magnitude and quantitative analysis is expected to be limited to around 5 percent without using complex fitting algorithms. Analysis of low concentration ions, at the ppm level, required a separate analysis using ion ejection techniques. Chemical ionization due to the formation of the MH{sup +} ion or MD{sup +} increased the complexity of the spectra compared to magnetic sector mass spectra and formation of the protonated or deuterated complex was a dynamic function of the trap ion concentration. This made quantitative measurement more of a challenge. However, the resolution of the instrument was far superior to any other mass spectrometry technique that has been applied to the analysis of the hydrogen isotopes. The piezo-electric picoliter injection device offers a new way of submitting small quantities of atmospheric pressure sample gas for analysis. The new software had many improvements over the previous version but significant flaws in the beta codes remain that make the prototype units less than ideal. The instrument is a promising new technology that experience will likely improve. Unfortunately, Siemens has concluded that the technology will not be a commercial success and has decided to stop producing this product.
Spencer, W; Laura Tovo, L
International Journal of Mass Spectrometry 260 (2007) 222�236 Extended data analysis strategies for high resolution imaging MS: New methods to deal with extremely large image hyperspectral datasets
The large size of the hyperspectral datasets that are produced with modern mass spectrometric imaging techniques makes it difficult to analyze the results. Unsupervised statistical techniques are needed to extract relevant information from these datasets and reduce the data into a surveyable overview. Multivariate statistics are commonly used for this purpose. Computational power and computer memory limit the resolution at which the datasets can be analyzed with these techniques. We introduce the use of a data format capable of efficiently storing sparse datasets for multivariate analysis. This format is more memory-efficient and therefore it increases the possible resolution together with a decrease of computation time. Three multivariate techniques are compared for both sparse-type data and non-sparse data acquired in two different imaging ToF-SIMS experiments and one LDI-ToF imaging experiment. There is no significant qualitative difference in the use of different data formats for the same multivariate algorithms. All evaluated multivariate techniques could be applied on both SIMS and the LDI imaging datasets. Principal component analysis is shown to be the fastest choice; however a small increase of computation time using a VARIMAX optimization increases the decomposition quality significantly. PARAFAC analysis is shown to be very effective in separating different chemical components but the calculations take a significant amount of time, limiting its use as a routine technique. An effective visualization of the results of the multivariate analysis is as important for the analyst as the computational issues. For this reason, a new technique for visualization is presented, combining both spectral loadings and spatial
Leendert A. Klerk A; Er Broersen B; Ian W. Fletcher C
The Ionizing Continuum of Quasars
The ionizing continuum shape of quasars is generally not directly observable, but indirect arguments, based on photoionization models and thin accretion disk models suggest that it should peak in the extreme UV, and drop steeply into the soft X-ray regime. However, recent observations of very soft X-ray emission in low z quasars, and far UV emission of high z quasars, suggest that the ionizing continuum of quasars does not peak in the extreme UV, and may extend as a single power law from ~1000 A to ~1 keV. If true, that has interesting implications for photoionization models and for accretion disk models. The proposed revised continuum shape will be tested directly in the near future with FUSE.
Ari Laor
The multiphoton ionization of uranium hexafluoride. Revision 1
Armstrong, D.P. [Oak Ridge K-25 Site, TN (United States). UEO Enrichment Technical Operations Div.] [Oak Ridge K-25 Site, TN (United States). UEO Enrichment Technical Operations Div.
Anal. Chem. 1981, 53, 1241-1244 1241 Comparison of Mass Spectra Obtained with Low-Energy Ion
and High-Energy Californium-252 Fission Fragment Bombardment Werner Ens and K. G. Standing Physics mass spectrometry (1,2)and low-energy ion bombardment mass spectrometry (3-5). In these techniquesAnal. Chem. 1981, 53, 1241-1244 1241 Comparison of Mass Spectra Obtained with Low-Energy Ion
Characterization of Ce SUP 3+-tributyl phosphate coordination complexes produced by fused droplet electrospray ionization with a target capillary
Coordination complexes containing Ce(III) and tri-n-butyl phosphate (TBP) in the 1+, 2+ and 3+ charge states were generated using desorption electrospray ionization (DESI) mass spectrometry, in which the analyte solutions were supplied via a target capillary orthogonally situated with respect to the electrospray. Comparison with direct electrospray (ESI) showed that the same coordination complexes were produced in each experiment, and could be described by the general formula [Ce(NO3)m=0-2(TBP)n](3-m)+. This result indicates that DESI has utility for measuring metal speciation for metal ligand solutions where the gas-phase complexes generated by ESI have been correlated with solution speciation. Such an application would be useful for analyses where it is desirable to limit the total amount of metal being handled, or that have solvent systems that are not readily amenable to ESI. Both the direct ESI and DESI mass spectra showed similar trends with respect to the TBP:Ce ratio, viz. high values tend to favor formation of a larger fraction of the 1+ species, and the 2+ and 3+ species become relatively more important as the ratio is decreased. Within individual charge state ion envelopes, lower TBP:Ce ratios produce coordination complexes with fewer ligands, a trend also seen using both approaches. These trends again point toward strong similarity between the direct ESI and DESI analyses of the metal-ligand solutions. The DESI experiments were less sensitive for measuring the coordination complexes compared to the direct ESI experiments, by a factor of 10 - 100 depending on whether minimum detectable concentration or absolute ion abundances were considered. Nevertheless, mid-picomolar quantities of coordination complexes were measured using the target capillary, indicating that sensitivity would be sufficient for measuring species in many industrial separations processes.
Gary S. Groenewold; Jean-Jacques Gaumet
Mass Spectral Molecular Networking of Living Microbial Colonies
Integrating the governing chemistry with the genomics and phenotypes of microbial colonies has been a "holy grail" in microbiology. This work describes a highly sensitive, broadly applicable, and costeffective approach that allows metabolic profiling of live microbial colonies directly from a Petri dish without any sample preparation. Nanospray desorption electrospray ionization mass spectrometry (MS), combined with alignment of MS data and molecular networking, enabled monitoring of metabolite production from live microbial colonies from diverse bacterial genera, including Bacillus subtilis, Streptomyces coelicolor, Mycobacterium smegmatis, and Pseudomonas aeruginosa. This work demonstrates that, by using these tools to visualize small molecular changes within bacterial interactions, insights can be gained into bacterial developmental processes as a result of the improved organization of MS/MS data. To validate this experimental platform, metabolic profiling was performed on Pseudomonas sp. SH-C52, which protects sugar beet plants from infections by specific soil-borne fungi [R. Mendes et al. (2011) Science 332:1097�1100]. The antifungal effect of strain SHC52 was attributed to thanamycin, a predicted lipopeptide encoded by a nonribosomal peptide synthetase gene cluster. Our technology, in combination with our recently developed peptidogenomics strategy, enabled the detection and partial characterization of thanamycin and showed that it is amonochlorinated lipopeptide that belongs to the syringomycin family of antifungal agents. In conclusion, the platform presented here provides a significant advancement in our ability to understand the spatiotemporal dynamics of metabolite production in live microbial colonies and communities.
Watrous, Jeramie D.; Roach, Patrick J.; Alexandrov, Theodore; Heath, Brandi S.; Yang, Jane Y.; Kersten, Roland; vander Voort, Menno; Pogliano, Kit; Gross, Harald; Raaijmakers, Jos M.; Moore, Bradley S.; Laskin, Julia; Bandeira, Nuno; Dorrestein, Pieter C.
The Cryogenic Dark Matter Search: First 5-Tower Data and Improved Understanding of Ionization Collection
The Cryogenic Dark Matter Search (CDMS) is searching for Weakly Interacting Massive Particles (WIMPs) with cryogenic particle detectors. These detectors have the ability to discriminate between nuclear recoil candidate and electron recoil background events by collecting both phonon and ionization energy from recoils in the detector crystals. The CDMS-II experiment has completed analysis of the first data runs with 30 semiconductor detectors at the Soudan Underground Laboratory, resulting in a world leading WIMP-nucleon spin-independent cross section limit for WIMP masses above 44 GeV/c{sup 2}. As CDMS aims to achieve greater WIMP sensitivity, it is necessary to increase the detector mass and discrimination between signal and background events. Incomplete ionization collection results in the largest background in the CDMS detectors as this causes electron recoil background interactions to appear as false candidate events. Two primary causes of incomplete ionization collection are surface and bulk trapping. Recent work has been focused on reducing surface trapping through the modification of fabrication methods for future detectors. Analyzing data taken with test devices has shown that hydrogen passivation of the amorphous silicon blocking layer worsens surface trapping. Additional data has shown that the iron-ion implantation used to lower the critical temperature of the tungsten transition-edge sensors causes a degradation of the ionization collection. Using selective implantation on future detectors may improve ionization collection for events near the phonon side detector surface. Bulk trappin