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Adapting to Evolving Business Environments Is...
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As Immunotherapy Revolutionizes the Cancer Treatment...
Wall Street Decline Takes Its Toll...
EMD Millipore took to the road for a European tour in a specially designed vehicle containing three laboratories that focus on pharmaceuticals, academic research, and food and beverage applications. Each of the three labs is complete with equipment to perform real experiments.
"Live Lab Tour was created because there are not any large lab shows like Analytica or Achema in the U.K.," says company spokesperson Sophie Pruvost. "We at Lab Solutions in EMD Millipore thought it would be ideal to showcase the products from these divisions and to demonstrate the company's offerings to our customers."
Equipment on the Live Lab Tour vehicle includes products for life science research to support scientists studying cell biology, stem cell biology, protein research, and cell signaling. The vehicle also houses a number of water purification systems.
"It's important to use the right type of water," explains Katie Molders of the firm's Lab Solutions division. "If you have too many organics in water, this can affect liquid chromatography applications, as you can have high background levels and ghost peaks. If you are performing experiments using florescence, it can decrease the amount of florescence detected. This is why it's useful to speak with scientists on this tour and show them the systems on display. We're able to advise them on the right choices for their application."
For scientists looking for the highest purity water, the Milli-Q® Integral water purification system includes Elix® technology. This generates both pressurized pure and ultrapure water directly from tap water. The system also includes separate points of delivery, which can be adapted with a final polisher to match specific research applications.
Also on the Live Lab Tour is a Direct-Q® water purification system with a space-saving remote dispenser for production of ultrapure water for critical applications, and the Elix Essential water purification system. The Elix has models with flow rates of 3, 5, 10, or 15 liters of pure water per hour. This system produces water suitable for use as a feed to laboratory equipment, in preparation of microbiological media, buffer, and pH solutions, and for manual glassware rinsing.
In addition to functioning as a set of mobile laboratories, the Live Lab Tour also offers an opportunity to book one-on-one meetings with an applications specialist to discuss optimizing protocols and improving laboratory workflow. During these meetings, experts are on hand to cover many of the important aspects to consider when implementing water purification or analytical systems.
They have on show TLC plates including the TLC LuxPlate® silica gel plates and HPLC columns in the Chromolith® range. They also explained some of the innovations the firm has made with the packaging in the Laboratory Essentials range, such as the Titripac® packaging system for ready-to-use TitriPUR® volumetric solutions.
The tour is visiting 10 science parks and institutions in Europe. Two more tour dates remain: June 12 in Darmstadt and June 14 in Martinsried. For more information, visit http://www.millipore.com/lab_water/cp1/live_lab_tour2012.
Sue Pearson, Ph.D., is GEN's European writer. She checked out EMD Millipore's Live Lab Tour last month.
Sue Pearson, Ph.D., is GEN's European writer. She checked out EMD Millipore's Live Lab Tour last month.
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While Zika continues to garner a lot of news coverage, a Mayo Clinic survey reveals that Americans believe the country's most significant healthcare challenge is cancer. Compared to other diseases, does the possibility of developing cancer worry you the most?
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Rent Learning about Plant Growth with Graphic Organizers 1st edition today, or search our site for other textbooks by Jonathan Kravetz. Every textbook comes with a 21-day "Any Reason" guarantee. Published by Rosen Publishing Group, Incorporated, The.
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October 28, 2013
New third quarter financials from the parcel delivery and freight-hauling giant UPS, show it doubled its profit in the third quarter of the year, coming in at $1.1 billion, compared with $469 million a year earlier.
Revenue came in at $13.5 billion, up 3.4% over the same time last year.
The Atlanta-based UPS delivered more than one billion packages worldwide in the third quarter, an increase of 4.6% over the prior-year period. Daily package volume growth was led by international export and U.S. domestic ground, up 6.7% and 3.0%, respectively.
In the company's supply chain and freight business, operating profit improved 7%, to $201 million and operating margin expanded 60 basis points, to 8.9%. Revenue in the segment was down slightly from the prior year period to $2.25 billion, as growth in UPS Freight was offset by declines in the forwarding business.
UPS Freight LTL revenue climbed 5.5% as a result of improved tonnage and rate increases. Operating margin for the business unit declined slightly, due to higher compensation and benefit expense.
More details are on the UPS website.
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"The Interview" Continues To Rake It In Online
This could be the birth of the online movie premiere.
ISIS is a growing cyber threat, but don't get too concerned about attacks on the Internet of Things just yet, according to business threat intelligence consultancy Flashpoint "Pro-ISIS hackers have emerged in the past two years with the intent to launch cyber-attacks on critical Western targets, and their numbers are growing," said Flashpoint co-founder Laith… Read more »
This could be the birth of the online movie premiere.
Also, North Korea just compared the U.S. President to a "monkey."
The things extremists worry about today could be mainstream concerns tomorrow.
Striking back at cyber criminals – so called "Strikeback" – carries serious risks that far outweigh the short-lived satisfaction of revenge.
The Pentagon has announced that it will increase the size of the U.S. Cyber Command. Despite a vague timeline, this move displays the fact that our modern warfare is moving in a more cyber direction. But are we ready to take it on?
ReadWrite sits down with candid technologist Bruce Schneier about digital feudalism, government regulations and the reality of cyber warfare.


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Polymer blend lithography: A versatile method to fabricate nanopatterned self-assembled monolayers
Huang, Cheng
Moosmann, Markus
Jin, Jiehong
Heiler, Tobias
Walheim, Stefan
Schimmel, Thomas
Beilstein Journal of Nanotechnology
A rapid and cost-effective lithographic method, polymer blend lithography (PBL), is reported to produce patterned self-assembled monolayers (SAM) on solid substrates featuring two or three different chemical functionalities. For the pattern generation we use the phase separation of two immiscible polymers in a blend solution during a spin-coating process. By controlling the spin-coating parameters and conditions, including the ambient atmosphere (humidity), the molar mass of the polystyrene (PS) and poly(methyl methacrylate) (PMMA), and the mass ratio between the two polymers in the blend solution, the formation of a purely lateral morphology (PS islands standing on the substrate while isolated in the PMMA matrix) can be reproducibly induced. Either of the formed phases (PS or PMMA) can be selectively dissolved afterwards, and the remaining phase can be used as a lift-off mask for the formation of a nanopatterned functional silane monolayer. This "monolayer copy" of the polymer phase morphology has a topographic contrast of about 1.3 nm. A demonstration of tuning of the PS island diameter is given by changing the molar mass of PS. Moreover, polymer blend lithography can provide the possibility of fabricating a surface with three different chemical components: This is demonstrated by inducing breath figures (evaporated condensed entity) at higher humidity during the spin-coating process. Here we demonstrate the formation of a lateral pattern consisting of regions covered with 1H,1H,2H,2H-perfluorodecyltrichlorosilane (FDTS) and (3-aminopropyl)triethoxysilane (APTES), and at the same time featuring regions of bare SiOx. The patterning process could be applied even on meter-sized substrates with various functional SAM molecules, making this process suitable for the rapid preparation of quasi two-dimensional nanopatterned functional substrates, e.g., for the template-controlled growth of ZnO nanostructures [1].
breath figure; nanopatterned template; polymer blend lithography (PBL); self-assembled monolayer (SAM); self assembly; spin coating; vapor phase
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Polymer blend lithography for metal films: large-area patterning with over 1 billion holes/inch2
Huang, Cheng
Förste, Alexander
Walheim, Stefan
Schimmel, Thomas
Beilstein Journal of Nanotechnology
Polymer blend lithography (PBL) is a spin-coating-based technique that makes use of the purely lateral phase separation between two immiscible polymers to fabricate large area nanoscale patterns. In our earlier work (Huang et al. 2012), PBL was demonstrated for the fabrication of patterned self-assembled monolayers. Here, we report a new method based on the technique of polymer blend lithography that allows for the fabrication of metal island arrays or perforated metal films on the nanometer scale, the metal PBL. As the polymer blend system in this work, a mixture of polystyrene (PS) and poly(methyl methacrylate) (PMMA), dissolved in methyl ethyl ketone (MEK) is used. This system forms a purely lateral structure on the substrate at controlled humidity, which means that PS droplets are formed in a PMMA matrix, whereby both phases have direct contact both to the substrate and to the air interface. Therefore, a subsequent selective dissolution of either the PS or PMMA component leaves behind a nanostructured film which can be used as a lithographic mask. We use this lithographic mask for the fabrication of metal patterns by thermal evaporation of the metal, followed by a lift-off process. As a consequence, the resulting metal nanostructure is an exact replica of the pattern of the selectively removed polymer (either a perforated metal film or metal islands). The minimum diameter of these holes or metal islands demonstrated here is about 50 nm. Au, Pd, Cu, Cr and Al templates were fabricated in this work by metal PBL. The wavelength-selective optical transmission spectra due to the localized surface plasmonic effect of the holes in perforated Al films were investigated and compared to the respective hole diameter histograms.
localized surface plasmonic resonance; metal islands; metal nanostructures; metal polymer blend lithography (metal PBL); nano-patterned template; nanoscale discs; optical transmission; perforated metal film; polymer phase separation; poly(methyl methacrylate) (PMMA); polystyrene (PS); self-assembly; spin-coating; surface plasmons
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Multi-technique Characterization of Self-assembled Carboxylic Acid Terminated Alkanethiol Monolayers on Nanoparticle and Flat Gold Surfaces
Techane, Sirnegeda D.
Gamble, Lara J.
Castner, David G.
The journal of physical chemistry. C, Nanomaterials and interfaces
Gold nanoparticles (AuNPs) with 14, 25 and 40nm diameters were functionalized with different chain length (C6, C8, C11 and C16) carboxylic acid terminated alkanethiol self-assembled monolayers (COOH-SAMs). X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used to examine the changes in surface chemistry as both AuNP diameter and SAM chain length were varied. COOH-SAMs on flat gold surfaces were also examined and compared to the COOH-SAM on AuNP results. For a given surface, as the COOH-SAM chain length increased the XPS C/Au atomic ratio increased due to an increased number of carbon atoms per molecule in the overlayer and an increased attenuation of the Au substrate signal. For the C16 COOH-SAMs, as the size of AuNPs decreased the XPS C/Au atomic ratio and the apparent SAM thickness increased due to the increased curvature of the smaller AuNPs. The C16 COOH-SAMs on the flat Au had the lowest XPS C/Au atomic ratio and apparent SAM thickness of any C16 COOH-SAM covered Au surface. The effective take-off angles of the COOH-SAMs were also calculated by comparing the apparent thickness of COOH-SAMs with literature values. The effective take-off angle for C16 COOH-SAM on 14nm, 25nm and 40nm diameter AuNPs and flat Au were found to be 57°, 53°, 51° and 39°, respectively, for data acquired in a mode that collects a wide range of photoelectron take-off angles. The effective take-off angle for C16 COOH-SAM on 14nm AuNP and flat Au decreased to 52° and 0°, respectively, for data acquired in a mode that collects a narrow range of photoelectron take-off angles. The ToF-SIMS results showed similar changes in surface chemistry with COOH-SAM chain length and AuNP size. For example, the ratio of the sum of the C1–4HxOy positive ion intensities to the sum of the Au-containing positive ions intensities increased with decreasing AuNP size and increasing COOH-SAM chain length. Fourier transform IR spectroscopy in the attenuated total reflectance mode (FTIR-ATR) was used to characterize the crystallinity of the COOH-SAMs. The CH2 stretching frequencies decreased with increasing COOH-SAM chain length on flat Au. The C16 COOH-SAM on the 14nm AuNPs exhibited a crystalline-like CH2 stretching frequency. The size, size distribution, shapes and solution stability of AuNPs were investigated with transmission electron microscopy (TEM) and UV/VIS spectroscopy. As the average diameter of the AuNPs decreased the size distribution became narrower and the shape became more spherical.
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Selective Binding, Self-Assembly and Nanopatterning of the Creutz-Taube Ion on Surfaces
Wang, Yuliang
Lieberman, Marya
Hang, Qingling
Bernstein, Gary
International Journal of Molecular Sciences
The surface attachment properties of the Creutz-Taube ion, i.e., [(NH3)5Ru(pyrazine)Ru(NH3)5]5+, on both hydrophilic and hydrophobic types of surfaces were investigated using X-ray photoelectron spectroscopy (XPS). The results indicated that the Creutz-Taube ions only bound to hydrophilic surfaces, such as SiO2 and –OH terminated organic SAMs on gold substrates. No attachment of the ions on hydrophobic surfaces such as –CH3 terminated organic SAMs and poly(methylmethacrylate) (PMMA) thin films covered gold or SiO2 substrates was observed. Further ellipsometric, atomic force microscopy (AFM) and time-dependent XPS studies suggested that the attached cations could form an inorganic analog of the self-assembled monolayer on SiO2 substrate with a "lying-down" orientation. The strong electrostatic interaction between the highly charged cations and the anionic SiO2 surface was believed to account for these observations. Based on its selective binding property, patterning of wide (∼200 nm) and narrow (∼35 nm) lines of the Creutz-Taube ions on SiO2 surface were demonstrated through PMMA electron resist masks written by electron beam lithography (EBL).
Creutz-Taube ions; Surface; Hydrophilic; Hydrophobic; XPS; AFM; Self-assembled Monolayers; E-beam lithography; PMMA; Nanopatterning
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Comparative Study of Electroless Copper Film on Different Self-Assembled Monolayers Modified ABS Substrate
Xu, Jiushuai
Fan, Ruibin
Wang, Jiaolong
Jia, Mengke
Xiong, Xuanrui
Wang, Fang
International Journal of Molecular Sciences
Copper films were grown on (3-Mercaptopropyl)trimethoxysilane (MPTMS), (3-Aminopropyl)triethoxysilane (APTES) and 6-(3-(triethoxysilyl)propylamino)-1,3,5- triazine-2,4-dithiol monosodium (TES) self-assembled monolayers (SAMs) modified acrylonitrile-butadiene-styrene (ABS) substrate via electroless copper plating. The copper films were examined using scanning electron microscopy (SEM) and X-ray diffraction (XRD). Their individual deposition rate and contact angle were also investigated to compare the properties of SAMs and electroless copper films. The results indicated that the formation of copper nuclei on the TES-SAMs modified ABS substrate was faster than those on the MPTMS-SAMs and APTES-SAMs modified ABS substrate. SEM images revealed that the copper film on TES-SAM modified ABS substrate was smooth and uniform, and the density of copper nuclei was much higher. Compared with that of TES-SAMs modified resin, the coverage of copper nuclei on MPTMS and APTES modified ABS substrate was very limited and the copper particle size was too big. The adhesion property test demonstrated that all the SAMs enhanced the interfacial interaction between copper plating and ABS substrate. XRD analysis showed that the copper film deposited on SAM-modified ABS substrate had a structure with Cu(111) preferred orientation, and the copper film deposited on TES-SAMs modified ABS substrate is better than that deposited on MPTMS-SAMs or APTES-SAMs modified ABS resins in electromigrtion resistance.
ABS resin; SAMs; electroless copper film; heterocyclic silane
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Electrochemical Characterization of Globotriose-Containing Self-Assembled Monolayers on Nanoporous Gold and their Binding of Soybean Agglutinin
Pandey, Binod
Tan, Yih Horng
Parameswar, Archana R.
Pornsuriyasak, Papapida
Demchenko, Alexei V.
Stine, Keith J.
Carbohydrate research
Self-assembled monolayers (SAMs) of α-D-Gal-(1→4)-β-D-Gal-(1→4)-β-D-Glc-mercaptooctane (globotriose, Gb3-C8-SH) were prepared both as single-component SAMs and as mixed SAMs with either octanethiol (OCT) or 8-mercapto-3,6-dioxaoctanol (HO-PEG2-SH), on flat gold and on nanoporous gold (NPG) electrodes. The binding of soybean agglutinin (SBA) to the globotriose (Gb3) unit in the SAMs was then studied using electrochemical impedance spectroscopy (EIS), which is a label free method found to be quite sensitive to SAM composition and to the differences in SAM structure on NPG versus on flat Au. The affinity of SBA to the mixed SAM of HO-PEG2-SH and Gb3-C8-SH on NPG is found to be greater on NPG than on flat gold, and indicates a potential advantage for NPG as a substrate. The SAMs of HO-PEG2-SH were found to resist protein adsorption on either NPG or flat gold. The non-specific adsorption of SBA to OCT SAMs on flat Au was observed in EIS by the increase in charge transfer resistance; whereas, the increase seen on the NPG surface was smaller, and suggests that EIS measurements on NPG are less affected by non-specific protein adsorption. Atomic force microscopy (AFM) images of the SBA binding to mixed SAM of HO-PEG2-SH and Gb3-C8-SH on NPG showed a greater number of proteins on top of the OCT containing SAMs.
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Fabrication of Interdigitated Micropatterns of Self-Assembled Polymer Nanofilms Containing Cell-adhesive Materials
Mohammed, Javeed Shaikh
DeCoster, Mark A.
McShane, Michael J.
Langmuir : the ACS journal of surfaces and colloids
Micropatterns of different biomaterials with micro- and nanoscale features and defined spatial arrangement on a single substrate are useful tools for studying cellular-level interactions, and recent reports have highlighted the strong influence of scaffold compliance in determining cell behavior. In this paper, a simple yet versatile and precise patterning technique for the fabrication of interdigitated micropatterns of nanocomposite multilayer coatings on a single substrate is demonstrated through a combination of lithography and layer-by-layer (LbL) assembly processes, termed as Polymer Surface Micromachining (PSM). The first nanofilm pattern is constructed using lithography, followed by LbL multilayer assembly and lift-off, and the process is repeated with optical alignment to obtain interdigitated patterns on the same substrate. Thus, the method is analogous to surface micromachining, except that the deposition materials are polymers and biological materials that are used to produce multilayer nanocomposite structures. A key feature of the multilayers is the capability to tune properties such as stiffness by appropriate selection of materials, deposition conditions, and post-deposition treatments. Two- and four-component systems on glass coverslips are presented to demonstrate the versatility of the approach to construct precisely-defined, homogeneous nanofilm patterns. In addition, an example of a complex system used as a testbed for in vitro cell adhesion and growth is provided: micropatterns of poly(sodium 4-styrenesulfonate)/poly-L-lysine hydrobromide (PSS/PLL) and secreted phospholipase A2/poly(ethyleneimine) (PEI/sPLA2) multilayers. The interdigitated square nanofilm array patterns were obtained on a single coverslip with poly(diallyldimethyl ammonium chloride) (PDDA) as a cell-repellent background. Cell culture experiments show that cortical neurons respond and bind specifically to the sPLA2 micropatterns in competition with PLL micropatterns. The fabrication and the initial biological results on the nanofilm micropatterns support the usefulness of the technique for use in studies aimed at elucidating important biological structure-function relationships, but the applicability of the fabrication method is much broader and may impact electronics, photonics, and chemical microsystems.
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Supramolecular Layer-by-Layer Assembly of 3D Multicomponent Nanostructures via Multivalent Molecular Recognition
Ling, Xing Yi
Phang, In Yee
Reinhoudt, David N.
Vancso, G. Julius
Huskens, Jurriaan
International Journal of Molecular Sciences
The supramolecular layer-by-layer assembly of 3D multicomponent nanostructures of nanoparticles is demonstrated. Nanoimprint lithography (NIL) was used as the patterning tool for making patterned β-cyclodextrin (CD) self-assembled monolayers (SAMs) and for the confinement of nanoparticles on the substrate. A densely packed and multilayered nanoparticle structure was created by alternating assembly steps of complementary guest- (Fc-SiO2, 60 nm) and host-functionalized (CD-Au, 3 nm) nanoparticles. The effects induced by the order of the nanoparticle assembly steps, going from large to small and from small to large nanoparticles by using Fc-SiO2, CD-Au, and CD-SiO2 (350 nm) nanoparticles, were compared. AFM height profiles revealed that the specific supramolecular assembly of nanoparticles was self-limited, i.e. one nanoparticle layer per assembly step, allowing the control over the thickness of the supramolecular hybrid nanostructure by choosing the size of the nanoparticles, irrespective of the core material of the nanoparticles. The roughness of structure, observed by AFM imaging of the top layer, was directly influenced by the size and packing of the underlying nanoparticle layers.
Supramolecular Chemistry; Layer-by-Layer Assembly; Nanoparticles; Nanoimprint lithography
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The Electronic Structure of Mixed Self-Assembled Monolayers
Rissner, Ferdinand
Egger, David A.
Romaner, Lorenz
Heimel, Georg
Zojer, Egbert
ACS Nano
The electronic structure of mixed self-assembled monolayers (SAMs) on Au(111) surfaces is modeled using slab-type density-functional theory calculations. The studied molecules have a dipolar character induced by polar and electron donating or accepting tail-group substituents. The resulting electronic structure of mixed layers is found to differ qualitatively from a simple superposition of those of the respective pure layers. Specifically, the positions of the frontier electronic states are shifted relative to the metal Fermi level, with the sign and magnitude of that shift depending on the dipole moment of the molecules and the mixing ratio in the film. This appears counterintuitive considering previous investigations, in which it has been shown that, for densely packed layers, tail-group substituents have no impact on the interfacial energy-level alignment. The seeming contradiction can be lifted by considering the local electrostatic interactions within the films in both mixed and homogeneous monolayers. Beyond that, we show that mixed SAMs provide an efficient tool for continuously tuning substrate work functions over a range that far exceeds that accessible by merely changing the coverage of homogeneous layers, with the net effect depending linearly on the mixing ratio in agreement with recent experimental findings.
self-assembled monolayer; metal−organic interface; quantum-mechanical modeling; band-structure calculation; mixed monolayer; heterogeneous surfaces; intermolecular interactions
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Nanoscale clustering of carbohydrate thiols in mixed SAMs on gold
Tantakitti, Faifan
Burk-Rafel, Jesse
Cheng, Fang
Egnatchik, Robert
Owen, Tate
Hoffman, Matt
Weiss, Dirk N.
Ratner, Daniel M.
Self-assembled monolayers (SAMs) bearing pendant carbohydrate functionality are frequently employed to tailor glycan-specific bioactivity onto gold substrates. The resulting glycoSAMs are valuable for interrogating glycan-mediated biological interactions via surface analytical techniques, microarrays, and label-free biosensors. GlycoSAM composition can be readily modified during assembly using mixed solutions containing thiolated species, including carbohydrates, oligo(ethylene glycol) (OEG) and other inert moieties. This intrinsic tunability of the self-assembled system is frequently used to optimize bioavailability and anti-biofouling properties of the resulting SAM. However, until now, our nanoscale understanding of the behavior of these mixed glycoSAMs has lacked detail. In this study, we examined the time-dependent clustering of mixed sugar+OEG glycoSAMs on ultraflat gold substrates. Composition and surface morphologic changes in the monolayers were analyzed by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), respectively. We provide evidence that the observed clustering is consistent with a phase separation process in which surface-bound glycans self-associate to form dense glycoclusters within the monolayer. These observations have significant implications for the construction of mixed glycoSAMs for use in biosensing and glycomics applications.
Atomic force microscopy; carbohydrates; glycoSAM; phase separation; XPS
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Effects of self-assembled monolayer structural order, surface homogeneity and surface energy on pentacene morphology and thin film transistor device performance
Hutchins, Daniel Orrin
Weidner, Tobias
Baio, Joe
Polishak, Brent
Acton, Orb
Cernetic, Nathan
Ma, Hong
Jen, Alex K.-Y.
Journal of materials chemistry. C, Materials for optical and electronic devices
A systematic study of six phosphonic acid (PA) self-assembled monolayers (SAMs) with tailored molecular structures is performed to evaluate their effectiveness as dielectric modifying layers in organic field-effect transistors (OFETs) and determine the relationship between SAM structural order, surface homogeneity, and surface energy in dictating device performance. SAM structures and surface properties are examined by near edge X-ray absorption fine structure (NEXAFS) spectroscopy, contact angle goniometry, and atomic force microscopy (AFM). Top-contact pentacene OFET devices are fabricated on SAM modified Si with a thermally grown oxide layer as a dielectric. For less ordered methyl- and phenyl-terminated alkyl ~(CH2)12 PA SAMs of varying surface energies, pentacene OFETs show high charge carrier mobilities up to 4.1 cm2 V−1 s−1. It is hypothesized that for these SAMs, mitigation of molecular scale roughness and subsequent control of surface homogeneity allow for large pentacene grain growth leading to high performance pentacene OFET devices. PA SAMs that contain bulky terminal groups or are highly crystalline in nature do not allow for a homogenous surface at a molecular level and result in charge carrier mobilities of 1.3 cm2 V−1 s−1 or less. For all molecules used in this study, no causal relationship between SAM surface energy and charge carrier mobility in pentacene FET devices is observed.
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Automated scanning probe lithography with n-alkanethiol self assembled monolayers on Au(111): Application for teaching undergraduate laboratories
Brown, Treva T.
LeJeune, Zorabel M.
Liu, Kai
Hardin, Sean
Li, Jie-Ren
Rupnik, Kresimir
Garno, Jayne C.
Journal of Laboratory Automation
Controllers for scanning probe instruments can be programmed for automated lithography to generate desired surface arrangements of nanopatterns of organic thin films, such as n-alkanethiol self-assembled monolayers (SAMs). In this report, atomic force microscopy (AFM) methods of lithography known as nanoshaving and nanografting are used to write nanopatterns within organic thin films. Commercial instruments provide software to control the length, direction, speed, and applied force of the scanning motion of the tip. For nanoshaving, higher forces are applied to an AFM tip to selectively remove regions of the matrix monolayer, exposing bare areas of the gold substrate. Nanografting is accomplished by force-induced displacement of molecules of a matrix SAM, followed immediately by the surface self-assembly of n-alkanethiol molecules from solution. Advancements in AFM automation enable rapid protocols for nanolithography, which can be accomplished within the tight time restraints of undergraduate laboratories. Example experiments with scanning probe lithography (SPL) will be described in this report that were accomplished by undergraduate students during laboratory course activities and research internships in the chemistry department of Louisiana State University. Students were introduced to principles of surface analysis and gained "hands-on" experience with nanoscale chemistry.
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Site-selective growth of surface-anchored metal-organic frameworks on self-assembled monolayer patterns prepared by AFM nanografting
Ladnorg, Tatjana
Welle, Alexander
Heißler, Stefan
Wöll, Christof
Gliemann, Hartmut
Beilstein Journal of Nanotechnology
Surface anchored metal-organic frameworks, SURMOFs, are highly porous materials, which can be grown on modified substrates as highly oriented, crystalline coatings by a quasi-epitaxial layer-by-layer method (liquid-phase epitaxy, or LPE). The chemical termination of the supporting substrate is crucial, because the most convenient method for substrate modification is the formation of a suitable self-assembled monolayer. The choice of a particular SAM also allows for control over the orientation of the SURMOF. Here, we demonstrate for the first time the site-selective growth of the SURMOF HKUST-1 on thiol-based self-assembled monolayers patterned by the nanografting technique, with an atomic force microscope as a structuring tool. Two different approaches were applied: The first one is based on 3-mercaptopropionic acid molecules which are grafted in a 1-decanethiolate SAM, which serves as a matrix for this nanolithography. The second approach uses 16-mercaptohexadecanoic acid, which is grafted in a matrix of an 1-octadecanethiolate SAM. In both cases a site-selective growth of the SURMOF is observed. In the latter case the roughness of the HKUST-1 is found to be significantly higher than for the 1-mercaptopropionic acid. The successful grafting process was verified by time-of-flight secondary ion mass spectrometry and atomic force microscopy. The SURMOF structures grown via LPE were investigated and characterized by atomic force microscopy and Fourier-transform infrared microscopy.
atomic force microscopy (AFM); metal-organic frameworks; nanografting; nanoshaving; SURMOF
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Instability of Self-Assembled Monolayers (SAM) as a Model Material System for Macrophage/FBGC Cellular Behavior
Jones, Jacqueline A.
Qin, L. Abby
Meyerson, Howard
Kwon, II Keun
Matsuda, Takehisa
Anderson, James M.
Journal of biomedical materials research. Part A
Novel self-assembled monolayers (SAMs) designed to present homogenous surface chemistries were utilized to further investigate the material surface chemistry dependent macrophage and foreign body giant cell (FBGC) behaviors including macrophage adhesion, fusion, and apoptosis. Contact angle analysis revealed instabilities in the –CH3 and –COOH terminate SAM surfaces upon incubation in serum-free media at 37oC or under dry, room temperatureconditions. Further analysis indicated that the –CH3 terminated SAM surface degraded rapidly within 2 hours and loss of sufficient SAM units to be comparable to the gold (Au) control surface within 24 hours of incubation in serum-free media (SFM) at 37oC. After 5days of incubation in SFM at 37oC, the contact angles for the –COOH terminated SAMsurfaces increased markedly. AFM analysis confirmed the desorption of –CH3 terminated SAM molecules from the surface with increased roughness and marked appearance of peaks andvalleys within 2 hours. A decrease in the thickness of the –COOH terminated SAM surface also suggests molecular desorption over time. No significant changes in contact angle or AFM analyses were observed on the –OH terminated SAM surfaces. Cellular adhesion decreased morerapidly on the Au control and –CH3 terminated SAM surfaces in comparison to the other surfaces. However by day 10, cellular adhesion, fusion, and apoptosis were comparable on all SAM surfaces and the Au control . These studies suggest that SAM surfaces may not be suitable for long-term studies where material dependent properties are investigated.
self-assembled monolayers; instability; macrophage; foreign body giant cell; contact angles
Related Articles
Effect of functional end groups of silane self assembled monolayer surfaces on apatite formation, fibronectin adsorption and osteoblast cell function
Toworfe, G.K.
Bhattacharyya, S.
Composto, R.J.
Adams, C.S.
Shapiro, I.M.
Ducheyne, P.
Journal of tissue engineering and regenerative medicine
Bioactive glass (BG) can directly bond to living bone without fibrous tissue encapsulation. Key mechanistic steps of BG's activity are attributed to calcium phosphate formation, surface hydroxylation and fibronectin (FN) adsorption. In the present study, self-assembled monolayers (SAMs) of alkanesilanes with different surface chemistry (OH, NH2, and COOH) were used as a model system to mimic BG's surface activity. Calcium phosphate (Ca-P) was formed on SAMs by immersion in a solution which simulates the electrolyte content of physiological fluids. FN adsorption kinetics and monolayer coverage was determined on SAMs with or without Ca-P coating. The surface roughness was also examined on these substrates before and after FN adsorption. The effects of FN-adsorbed, Ca-P coated SAMs on the function of MC3T3-E1 were evaluated by cell growth, expression of alkaline phosphatase activity, and actin cytoskeleton formation. We demonstrate that, although the FN monolayer coverage and the rms roughness are similar on −OH and −COOH terminated SAMs with or without Ca-P coating, higher levels of ALP activity, more actin cytoskeleton formation and more cell growth are obtained on −OH and −COOH terminated SAMs with Ca-P coating. In addition, although the FN monolayer coverage is higher on Ca-P coated −NH2 terminated SAMs and SiOx surfaces, higher levels of ALP activity and more cell growth are obtained on Ca-P coated −OH and −COOH terminated SAMs. Thus with same Ca-P coatings, different surface functional groups have different effects on the function of osteoblastic cells. These findings represent new insights into the mechanism of bioactivity of BG and, thereby, may lead to designing superior constructs for bone grafting.
self assembled monolayers; calcium phosphate; protein adsorption; cell attachment; proliferation; alkaline phosphatase activity
Related Articles
Template-Stripped Smooth Ag Nanohole Arrays with Silica Shells for Surface Plasmon Resonance Biosensing
Im, Hyungsoon
Lee, Si Hoon
Wittenberg, Nathan J.
Johnson, Timothy W.
Lindquist, Nathan C.
Nagpal, Prashant
Norris, David J.
Oh, Sang-Hyun
ACS nano
Inexpensive, reproducible and high-throughput fabrication of nanometric apertures in metallic films can benefit many applications in plasmonics, sensing, spectroscopy, lithography and imaging. Here we use template stripping to pattern periodic nanohole arrays in optically thick, smooth Ag films with a silicon template made via nanoimprint lithography. Ag is a low-cost material with good optical properties, but it suffers from poor chemical stability and biocompatibility. However, a thin silica shell encapsulating our template-stripped Ag nanoholes facilitates biosensing applications by protecting the Ag from oxidation as well as providing a robust surface that can be readily modified with a variety of biomolecules using well-established silane chemistry. The thickness of the conformal silica shell can be precisely tuned by atomic layer deposition, and a 15-nm-thick silica shell can effectively prevent fluorophore quenching. The Ag nanohole arrays with silica shells can also be bonded to polydimethylsiloxane (PDMS) microfluidic channels for fluorescence imaging, formation of supported lipid bilayers, and real-time, label-free SPR sensing. Additionally, the smooth surfaces of the template-stripped Ag films enhance refractive index sensitivity compared with as-deposited, rough Ag films. Because nearly centimeter-sized nanohole arrays can be produced inexpensively without using any additional lithography, etching or lift-off, this method can facilitate widespread applications of metallic nanohole arrays for plasmonics and biosensing.
Template stripping; plasmonics; surface plasmon resonance; nanohole array; atomic; layer deposition; microfluidics; biosensing; nanoimprint lithography; supported lipid bilayer
Related Articles
Biosensor for human IgE detection using shear-mode FBAR devices
Chen, Ying-Chung
Shih, Wei-Che
Chang, Wei-Tsai
Yang, Chun-Hung
Kao, Kuo-Sheng
Cheng, Chien-Chuan
Nanoscale Research Letters
Film bulk acoustic resonators (FBARs) have been evaluated for use as biosensors because of their high sensitivity and small size. This study fabricated a novel human IgE biosensor using shear-mode FBAR devices with c-axis 23°-tilted AlN thin films. Off-axis radio frequency (RF) magnetron sputtering method was used for deposition of c-axis 23°-tilted AlN thin films. The deposition parameters were adopted as working pressure of 5 mTorr, substrate temperature of 300°C, sputtering power of 250 W, and 50 mm distance between off-axis and on-axis. The characteristics of the AlN thin films were investigated by X-ray diffraction and scanning electron microscopy. The frequency response was measured with an HP8720 network analyzer with a CASCADE probe station. The X-ray diffraction revealed (002) preferred wurtzite structure, and the cross-sectional image showed columnar structure with 23°-tilted AlN thin films. In the biosensor, an Au/Cr layer in the FBAR backside cavity was used as the detection layer and the Au surface was modified using self-assembly monolayers (SAMs) method. Then, the antigen and antibody were coated on biosensor through their high specificity property. Finally, the shear-mode FBAR device with kt2 of 3.18% was obtained, and the average sensitivity for human IgE detection of about 1.425 × 105 cm2/g was achieved.
AlN; Shear mode; FBAR; Biosensor
Related Articles
Substrate-mediated effects in photothermal patterning of alkanethiol self-assembled monolayers with microfocused continuous-wave lasers
Schröter, Anja
Kalus, Mark
Hartmann, Nils
Beilstein Journal of Nanotechnology
In recent years, self-assembled monolayers (SAMs) have been demonstrated to provide promising new approaches to nonlinear laser processing. Most notably, because of their ultrathin nature, indirect excitation mechanisms can be exploited in order to fabricate subwavelength structures. In photothermal processing, for example, microfocused lasers are used to locally heat the substrate surface and initiate desorption or decomposition of the coating. Because of the strongly temperature-dependent desorption kinetics, the overall process is highly nonlinear in the applied laser power. For this reason, subwavelength patterning is feasible employing ordinary continuous-wave lasers. The lateral resolution, generally, depends on both the type of the organic monolayer and the nature of the substrate. In previous studies we reported on photothermal patterning of distinct types of SAMs on Si supports. In this contribution, a systematic study on the impact of the substrate is presented. Alkanethiol SAMs on Au-coated glass and silicon substrates were patterned by using a microfocused laser beam at a wavelength of 532 nm. Temperature calculations and thermokinetic simulations were carried out in order to clarify the processes that determine the performance of the patterning technique. Because of the strongly temperature-dependent thermal conductivity of Si, surface-temperature profiles on Au/Si substrates are very narrow ensuring a particularly high lateral resolution. At a 1/e spot diameter of 2 µm, fabrication of subwavelength structures with diameters of 300–400 nm is feasible. Rapid heat dissipation, though, requires high laser powers. In contrast, patterning of SAMs on Au/glass substrates is strongly affected by the largely distinct heat conduction within the Au film and in the glass support. This results in broad surface temperature profiles. Hence, minimum structure sizes are larger when compared with respective values on Au/Si substrates. The required laser powers, though, are more than one order of magnitude lower. Also, the laser power needed for patterning decreases with decreasing Au layer thickness. These results demonstrate the impact of the substrate on the overall patterning process and provide new perspectives in photothermal laser patterning of ultrathin organic coatings.
femtosecond lasers; nonlinear laser processing; self-assembled monolayers; subwavelength patterning; ultrathin resists
Related Articles
The oriented and patterned growth of fluorescent metal–organic frameworks onto functionalized surfaces
Zhuang, Jinliang
Friedel, Jasmin
Terfort, Andreas
Beilstein Journal of Nanotechnology
A metal–organic framework (MOF) material, [Zn2(adc)2(dabco)] (adc = anthracene-9,10-dicarboxylate, dabco = 1,4-diazabicyclo[2.2.2]octane), the fluorescence of which depends on the loading of its nanopores, was synthesized in two forms: as free-flowing nanocrystals with different shapes and as surface-attached MOFs (SURMOFs). For the latter, we used self-assembled monolayers (SAMs) bearing functional groups, such as carboxylate and pyridyl groups, capable of coordinating to the constituents of the MOF. It could be demonstrated that this directed coordination also orients the nanocrystals deposited at the surface. Using two different patterning methods, i.e., microcontact printing and electron-beam lithography, the lateral distribution of the functional groups could be determined in such a way that the highly localized deposition of the SURMOF films became possible.
electron-beam lithography; irradiation-promoted exchange reaction; microcontact printing; radiation-induced nanostructure; self-assembled monolayer; surface-attached metal–organic framework
Related Articles
Simulation and Modeling of Self-Assembled Monolayers of Carboxylic Acid Thiols on Flat and Nanoparticle Gold Surfaces
Techane, Sirnegeda
Baer, Donald R.
Castner, David G.
Analytical chemistry
Quantitative analysis of the 16-mercaptohexadecanoic acid self-assembled monolayer (C16 COOH-SAM) layer thickness on gold nanoparticles (AuNPs) was performed using simulation of electron spectra for surface analysis (SESSA) software and x-ray photoelectron spectroscopy (XPS) experimental measurements. XPS measurements of C16 COOH SAMs on flat gold surfaces were made at 9 different photoelectron emission angles (5° to 85° in 10° increments), corrected using geometric weighting factors and then summed together to approximate spherical AuNPs. The SAM thickness and relative surface roughness (RSA) in SESSA were optimized to determine the best agreement between simulated and experimental surface composition. Based on the glancing-angle results, it was found that inclusion of a hydrocarbon contamination layer on top the C16 COOH-SAM was necessary to improve the agreement between the SESSA and XPS results. For the 16 COOH-SAMs on flat Au surfaces, using a SAM thickness of 1.1Å/CH2 group, an RSA of 1.05, and a 1.5Å CH2-contamination overlayer (total film thickness = 21.5Å) for the SESSA calculations provided the best agreement with the experimental XPS data. After applying the appropriate geometric corrections and summing the SESSA flat-surface compositions, the best fit results for the 16 COOH-SAM thickness and surface roughness on the AuNPs indicated a slightly thinner overlayer with parameters of 0.9Å/CH2 group in the SAM, a RSA of 1.06 RSA and a 1.5Å CH2-contamination overlayer (total film thickness = 18.5Å). The three angstrom difference in SAM thickness between the flat Au and AuNP surfaces suggests that the alkyl chains of the SAM are slightly more tilted or disordered on the AuNP surfaces.
Related Articles
Nanoscale patterning of a self-assembled monolayer by modification of the molecule–substrate bond
Shen, Cai
Buck, Manfred
Beilstein Journal of Nanotechnology
The intercalation of Cu at the interface of a self-assembled monolayer (SAM) and a Au(111)/mica substrate by underpotential deposition (UPD) is studied as a means of high resolution patterning. A SAM of 2-(4'-methylbiphenyl-4-yl)ethanethiol (BP2) prepared in a structural phase that renders the Au substrate completely passive against Cu-UPD, is patterned by modification with the tip of a scanning tunneling microscope. The tip-induced defects act as nucleation sites for Cu-UPD. The lateral diffusion of the metal at the SAM–substrate interface and, thus, the pattern dimensions are controlled by the deposition time. Patterning down to the sub-20 nm range is demonstrated. The difference in strength between the S–Au and S–Cu bond is harnessed to develop the latent Cu-UPD image into a patterned binary SAM. Demonstrated by the exchange of BP2 by adamantanethiol (AdSH) this is accomplished by a sequence of reductive desorption of BP2 in Cu free areas followed by adsorption of AdSH. The appearance of Au adatom islands upon the thiol exchange suggests that the interfacial structures of BP2 and AdSH SAMs are different.
copper; electrodeposition; gold adatoms; nanolithography; negative resist
Related Articles
Modulation of electrochemical hydrogen evolution rate by araliphatic thiol monolayers on gold
Muglali, Mutlu I.
Erbe, Andreas
Chen, Ying
Barth, Christoph
Koelsch, Patrick
Rohwerder, Michael
Electrochimica acta
Electroreductive desorption of a highly ordered self-assembled monolayer (SAM) formed by the araliphatic thiol (4-(4-(4-pyridyl)phenyl)phenyl)methanethiol leads to a concurrent rapid hydrogen evolution reaction (HER). The desorption process and resulting interfacial structure were investigated by voltammetric techniques, in situ spectroscopic ellipsometry, and in situ vibrational sum–frequency–generation (SFG) spectroscopy. Voltammetric experiments on SAM-modified electrodes exhibit extraordinarily high peak currents, which di er between Au(111) and polycrystalline Au substrates. Association of reductive desorption with HER is shown to be the origin of the observed excess cathodic charges. The studied SAM preserves its two–dimensional order near Au surface throughout a fast voltammetric scan even when the vertex potential is set several hundred millivolt beyond the desorption potential. A model is developed for the explanation of the observed rapid HER involving ordering and pre–orientation of water present in the nanometer–sized reaction volume between desorbed SAM and the Au electrode, by the structurally extremely stable monolayer, leading to the observed catalysis of the HER.
Reductive SAM desorption; Hydrogen evolution; Catalysis; Sum frequency generation spectroscopy; Spectroscopic ellipsometry
Related Articles
Stability of Phosphonic Self Assembled Monolayers (SAMs) on Cobalt Chromium (Co-Cr) Alloy under Oxidative conditions
Bhure, Rahul
Abdel-Fattah, Tarek M.
Bonner, Carl
Hall, Felicia
Mahapatro, Anil
Applied surface science
Cobalt Chromium (Co-Cr) alloys has been widely used in the biomedical arena for cardiovascular, orthopedic and dental applications. Surface modification of the alloy allows us to tailor the interfacial properties to address critical challenges of Co-Cr alloy in medical applications. Self assembled monolayers (SAMs) of Octadecylphosphonic acid (ODPA) have been used to form thin films on the oxide layer of the Co-Cr alloy surface by solution deposition technique. The SAMs formed were investigated for their stability to oxidative conditions of ambient laboratory environment over periods of 1, 3, 7 and 14 days. The samples were then characterized for their stability using X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM) and Contact Angle Measurements. Detailed high energy XPS elemental scans confirmed the presence of the phosphonic monolayer after oxidative exposure which suggested that the SAMs were firmly attached to the oxide layer of Co-Cr alloy. AFM images gave topographical data of the surface and showed islands of SAMs on Co-Cr alloy surface, before and after SAM formation and also over the duration of the oxidative exposure. Contact angle measurements confirmed the hydrophobicity of the surface over 14 days. Thus the SAMs were found to be stable for the duration of the study. These SAMs could be subsequently tailored by modifying the terminal functional groups and could be used for various potential biomedical applications such as drug delivery, biocompatibility and tissue integration
surface modification; self assembled monolayers (SAMs); phosphonic acids; cobalt chromium alloy
Related Articles
Structure and Order of Phosphonic Acid-Based Self-Assembled Monolayers on Si(100)
Dubey, Manish
Weidner, Tobias
Gamble, Lara J.
Castner, David G.
Langmuir : the ACS journal of surfaces and colloids
Organophosphonic acid self-assembled monolayers (SAMs) on oxide surfaces have recently seen increased use in electrical and biological sensor applications. The reliability and reproducibility of these sensors require good molecular organization in these SAMs. In this regard, packing, order and alignment in the SAMs is important, as it influences the electron transport measurements. In this study, we examine the order of hydroxyl- and methyl- terminated phosphonate films deposited onto silicon oxide surfaces by the tethering by aggregation and growth method using complementary, state-of-art surface characterization tools. Near edge x-ray absorption fine structure (NEXAFS) spectroscopy and in situ sum frequency generation (SFG) spectroscopy are used to study the order of the phosphonate SAMs in vacuum and under aqueous conditions, respectively. X-ray photoelectron spectroscopy and time of flight secondary ion mass spectrometry results show that these samples form chemically intact monolayer phosphonate films. NEXAFS and SFG spectroscopy showed that molecular order exists in the octadecylphosphonic acid and 11-hydroxyundecylphosphonic acid SAMs. The chain tilt angles in these SAMs were approximately 37° and 45°, respectively.
Phosphonic acid; T-BAG method; NEXAFS; SFG; ToF-SIMS; XPS; surface analysis; order; SAM
Related Articles
Selective Filling of Nanowells in Nanowell Arrays Fabricated Using Polystyrene Nanosphere Lithography with Cytochrome P450 Enzymes
Wollenberg, Lance A.
Jett, John E.
Wu, Yueting
Flora, Darcy R.
Wu, Nianqiang
Tracy, Timothy S.
Gannett, Peter M.
This work describes an original and simple technique for protein immobilization into nanowells, fabricated using nanopatterned-array fabrication methods, while ensuring the protein retains the normal biological activity. Nanosphere-lithography was used to fabricate a nanowell array with nanowells that were 100 nm in diameter and a periodicity of 500 nm. The base of the nanowells was gold and the surrounding material was silicon dioxide. The different surface chemistries of these materials were used to attach two different self-assembled monolayers (SAM) with different affinities for the protein used here, cytochrome P450 (P450). The nanowell SAM, a methyl terminated thiol, had high affinity for the P450. The surrounding SAM, a polyethylene glycol silane, displayed very little affinity toward the P450 isozyme CYP2C9, as demonstrated by x-ray photoelectron spectroscopy and surface plasmon resonance. The regularity of the nanopatterned array was examined by scanning electron microscopy and atomic force microscopy. P450-mediated metabolism experiments of known substrates demonstrated that the nanowell bound P450 enzyme exceeded its normal activity, as compared to P450 solutions, when bound to the methyl terminated self-assembled monolayer. The nanopatterned array chips bearing P450 display long term stability and give reproducible results making them potentially useful for high throughput screening assays or as nanoelectrode arrays.
Nanowell array; Self-assembled monolayer; cytochrome P450
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Old English Bulldog Pups, pups come with Purebred Papers, shots, shot Records and have Been Dewormed. Parents on Premise with no health issues. $900 call 732-489-9222 if interested. NO EMAILS, Thanks
Aug 30 -
Atlantic City :
Toms River - Dogs & puppies
Puppies are registered, will be ready in about 1.5 weeks
Pups are 6.5 weeks old
There are two litters to different moms
Hemi is white with brindle patches, Smurfet is white with blue fawn patches. Males n females. Moms are both about 50lbs and dad is blue fawn brindle 75lb beast.
Parents have great temperments. Puppies will come with shots and deworming. Please email for more details and ...
Aug 30 -
Boston :
Northborough - Dogs & puppies
This is Osiris. He is a smart, energetic, athletic guy. Good with kids and other dogs. He is $375 with no papers or $450 with them. If you are interested please email!
Aug 30 -
Hagerstown-Martinsburg :
Altoona - Dogs & puppies
The mama is half English Mastiff half Olde English Bulldog. The Sire is an AKC English Mastiff. The Olde Bulldog side comes from great IOEBA/CKC bloodlines. Puppies will come UTD on shots/dewormings and they are 11 wks old. Puppies will top out at around 120 pounds. There are 4 females still available out of 11 puppies. If you are interested please email for more pics of the pups, parents ...
Aug 30 -
Harrisburg :
State College - Dogs & puppies
Chocolate Tri Baby Girl
Taking deposit on IEOBA Olde English Bulldogge puppy.Will be ready October 7.All pups come with IOEBA reg papers, Health certificate, including first shots, worming, and tails docked. We have a five generation pedigree, one Year Health Warranty, puppy kit and a lifetime of support from us! We breed each of our puppies for excellent health and ...
Aug 30 -
Central New York :
Syracuse - Dogs & puppies
Miss Marilyn or "Marilyn Monroe" as we call her is available. She displays an amazing rope, wrinkles and is short and stocky. She is the sweetest little girl and enjoys attention, sitting on laps, playing in the water bowl and picking on her step brothers. She is 10 weeks old and ready to go to her forever home! She has had 2 sets of vaccines and all wormings up to date. She is available to a ...
Aug 30 -
Rhode Island :
Smithfield - Dogs & puppies
We have a few puppies still available. Our puppies are hand raised with the entire family helping including our 6 children. Parents are on site with us and we have great health history behind them. In many cases we own grandchildren of some of our dogs. All our puppies will have 1st shots, deworming, tails docked, vet checked, and health certificate before leaving. Our puppies also come with ...
Aug 27 -
Hartford :
Enfield - Dogs & puppies
We have four puppies left from our August litter. All puppies will have 1st shots, dewormings, tails docked, vet checked and health certificate. there are 3 boys and one girl left. They will be ready to go on Oct 4th when 8 weeks old.
All our puppies are hand raised with the entire family helping. Socialized around kids from ages 3 to teenagers. here the entire family helps is raising our ...
Aug 27 -
New Hampshire :
Hooksett - Dogs & puppies
We have pure bred generatíonal old English bulldogge puppies!! Registerd..She had 8!!! 6 avail ! 2 girls, 4 boys...Blue ,tan ,brindle... Beautiful!!! We r located in NH ..will consider shipping ,at your cost. Serious buyers only , our time is precious and spent on these beauties.. 500.00 deposit. They will have health check ,docked tail,up to date on shots and puppy papers.....!!! so ...
Aug 27 -
Boston :
Manchester - Dogs & puppies
We have a new litter just over three weeks old. They will be ready to go first week in October when 8 weeks old. Litter was 8 and we still have 4 puppies available. colors are blue fawn, blue tri, and blue seal. Parents are on site with us and puppies are hand raised with the entire family helping including our 6 children. All puppies are well socialized around other dogs, children, and loud ...
Aug 26 -
Boston :
Malden - Dogs & puppies
We have Blue Merle and Merle Olde English Bulldogges for sale.
All are pups born and raised in our home, and will be well socialized, IOEBA registered, up to date on shots, wormings, with tails and dew claws removed. We stand behind all dogs we produce and offer continued support. No dog will leave us without a full veterinary exam.They receive daily exercise and training, and can be taken ...
Aug 25 -
Rochester (NY) :
Bloomfield - Dogs & puppies
Beautiful Olde English Bulldogge/Boxeer mix puppies! Rainbow of colors! I own mom and dad. They have amazing personalities and temperament. Family raised, tails/dews done, worming and shots and vet visit at 8 weeks old. I encourage weekly visits to create a bond with your new puppy. Taking deposits now! They are ready to go to their furever homes on 9/7/16.
Aug 25 -
Portland (ME) :
Windham - Dogs & puppies
Up for sale is an adorable female English bulldog puppy for sale. Up to date on shots and dewormed. We want them to go to a loving home. Very playful and cuddly and follows you everywhere. Price is $1800 To a loving home only.
7 weeks old
Please call or text.
Located in Queens NY
Aug 24 -
New York City :
Astoria - Dogs & puppies
I have a beautiful full bred Bulldog puppy. She is 7 weeks old and a female
Health certification from licences vet. Has age appropriate shots Very energetic, playful and attention seeking companion. She is great with children, cats, other dog and displays no aggression for food or toys.
Any questions are welcomed, additional pictures for serious buyers, I will skype or face time with you so ...
excellent family member, loves cats, dogs, and children. he is not neutered, has papers, is trained. cost me $3k, moving now. these dogs don't have health issues like regular bulldogs and are adaptable to any new situations. he is two years old so no surprises.
OEB olde english bulldogge
This ad was posted with the eBay Classifieds mobile app.
Aug 24 -
Fairfield :
Nanuet - Dogs & puppies
Olde English bulldoggee pups
-18 month health warranty
-Current on all vaccines and worm prevention
-ioeba paperwork
Sire :El uno di Scarface (America first and only direct bullforce Scarface son.Scarface is located in europe. )
Dame:northstars sadie
Please call or text
Aug 24 -
New York City :
New York - Dogs & puppies
These are NOT English bulldogs.
They are 2 different breeds.
Olde English bulldogges
Born 8/10/16
Taking deposits
2 girls $700
Ioeba registered
Parents on site
tails docked
Will be vet checked at 6 weeks old which includes 1st shots and worming along with health physical done by vet.
Pictures were just updated 8/16/16
Will be ready the 1st week in October.
$100 nonrefundable deposit
Payment ...
Aug 23 -
Dutch Country PA :
Red Lion - Dogs & puppies
2 Beautiful boys for you to choose from. 6 weeks old. Ready now.
Vet checked and health certified. Wormed and shots. AKC papers. Call for appointment to come and see them.
Aug 22 -
Rochester (NY) :
Hamlin - Dogs & puppies
New pups are here
I have 2 authentic purebred English Bulldog puppies that are in need of a permanent loving home . They are 10 week old female and 10 week old male. They are up to date on all shots , deworming health certification. If you are interested in one of puppies and understand the quality of this breed please feel free to call or text me for details.
$1800 for 1
$3500 for 2
Aug 21 -
Boston :
Wakefield - Dogs & puppies
4 Year old black/white Olde English Bulldogge male available to a good home. This handsome boy is around 75 lbs, not neutered and has sired a few litters. He is IOEBA and CKC registered. He is housebroken and is good with children, but due to his size we DO NOT recommend him go to a home with children under 8 years old as he may knock them over. He is good with other dogs as long as they are ...
Aug 18 -
Baltimore :
Greenbelt - Dogs & puppies
I have Old English Bulldog puppies for sale. I'm selling my puppies as pets. They will be ready on the first week of October. For more info Email me.
Only males no females available. Thanks
Aug 18 -
New York City :
Hempstead - Dogs & puppies
These are NOT English bulldogs.
They are 2 different breeds.
Born 8/10/16
Taking deposits
3 girls $700
Ioeba registered
Parents on site
tails docked
Will be vet checked at 6 weeks old which includes 1st shots and worming along with health physical done by vet.
Pictures were just updated 8/16/16
Will be ready the 1st week in October.
$100 nonrefundable deposit
Payment plans available
717 ...
Aug 18 -
Dutch Country PA :
Red Lion - Dogs & puppies
We just had a litter of 7 precious puppies, which arrived on July 14, 2016. We had 5 males and 2 females. We still have 1 FEMALE available. They we be ready to leave us and settle into their new forever homes on September 9, 2016. We are accepting deposits at this time . Puppies will come with there first puppy shot, docked tails, de wormed, registration, and a 1 year health guarantee. Our ...
Aug 17 -
Boston :
Portsmouth - Dogs & puppies
We just had a litter of 7 lovely puppies, which arrived on July 14, 2016. We had 5 males and 2 females. Their is still 1 FEMALE available.They we be ready to leave us and settle into their new forever homes on September 9, 2016. Puppies will come with there first puppy shot, docked tails, de wormed, registration, and a 1 year health guarantee. Our main objective is to produce Bulldogs with ...
Aug 17 -
Hartford :
Hartford - Dogs & puppies
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A Little Jane Silver Adventure
A Little Jane Silver Adventure (Book 1)Meet Little Jane Silver, the twelve year-old granddaughter of notorious Treasure Island pirate Long John Silver. Growing up on the Pieces of Eight, the pirate ship of her parents, Captains Bonnie Mary Bright and Long John Silver II, Little Jane is increasingly frustrated with being thrust below decks whenever any real pirating action takes place. Desperate to be taken seriously as a member of the
Little Jane and the Nameless Isle
A Little Jane Silver Adventure
A Little Jane Silver Adventure (Book 2)Only two people have ever survived a trip to the Nameless Isle: Long John Silver the Second and Bonnie Mary Bright, the parents of aspiring pirate Little Jane Silver. They thought the volcanic caves on the island would be great places to store their treasure, but they were mistaken.Pirate hunter Fetzcaro Madsea and his crew have taken Long John and Bonnie Mary prisoner and are now forcing the
The Little Jane Silver 2-Book Bundle
Little Jane Silver / Little Jane and the Nameless Isle
A Little Jane Silver Adventure (Book 3)Presenting both of Little Jane Silver's piratical adventures in one special bundle! Little Jane Silver is the granddaughter of the notorious pirate Long John Silver. Growing up on her parents' ship, she vows to become a real pirate. As her ship is pursued by a mysterious pirate hunter, and on her own for the first time, Little Jane must grow up fast and find the courage to undergo the most
$25.99The stunning Hunger Games trilogy is complete! The extraordinary, ground breaking New York Times bestsellers The Hunger Games and Catching Fire, along with the third book in The Hunger Games trilogy by Suzanne Collins, Mockingjay, are available for the first time ever in e-book. Stunning, gripping, and powerful. The trilogy is now complete!
$6.29On the run in a stolen car with a kidnapped baby in tow Custis Curl and Boobie are three young people with deeply troubled pasts and bleak futures. As they struggle to find a new life for themselves it becomes painfully clear that none of them will ever be able to leave the past behind. Yet for one redemption is waiting in the unlikeliest of places. With the raw language of the street and lyrical
$13.59When your mom thinks she's Amelia Earhart, navigating high school, first love, and family secrets is like flying solo without a map. Driver's ed and a first crush should be what Alex Winchester is stressed out about in high school — and she is. But what's really on her mind is her mother. Why is she dressing in Dad's baggy khaki pants with a silk scarf around her neck? What is she planning when
$9.99Sixteen-year-old Jared is the newly crowned Prince of All Archenfield, ascending the throne after his older brother's mysterious death. But Jared feels reluctant and unprepared to rule the Princedom and its dangerous and powerful court. Like each Prince of All Archenfield before him, Jared must rely on the Council of Twelve to advise him. But he knows he can just as easily be at their mercy-
$8.092013 Information Book Awards — Long-listed Peace after the First World War inspires hope for a better life that's crushed by the advent of the Second World War. Beginning with the Treaty of Versailles and the hope for the birth of a better world, Failed Hope follows the postwar rise of fascism, social unrest, Prohibition, the Great Depression, Adolf Hitler's rise to power, and the wars in
The Wild Place Adventure Series (Book 1)Twelve-year-old Robin will never get over her mother's death. Nor will she forgive her father for moving the family to a small town to live with a weird grandmother. At her new school Robin is laughingly called "Green Girl" and is taunted relentlessly because of an award she received. She decides not to care about anyone or anything. But when her pregnant dog plunges into the frozen lake, she
$6.99Ten-year-old Sugar lives on the River Road sugar plantation along the banks of the Mississippi. Slavery is over, but laboring in the fields all day doesn't make her feel very free. Thankfully, Sugar has a knack for finding her own fun, especially when she joins forces with forbidden friend Billy, the white plantation owner's son. Sugar has always yearned to learn more about the world, and she
$11.99Charlie can't wait for school to be over. But he's wondering what particular vacation ordeal his parents have lined up for the family this summer. Canoeing with alligators in Okefenokee? Getting caught in the middle of a revolutionary shootout in Mexico? Or perhaps another trip abroad? Turns out, this summer the family is staying put, in their hometown. Montreal, Canada. A "staycation," his
$8.99With a "headstrong heroine on par with Katniss Everdeen and Tris Prior" (Kirkus) this debut thriller combines a pulse-pounding scifi thriller with a new adult coming-of-age story set at Texas A&M University. When Ren Sharpe was fourteen, she was kidnapped by a shadowy organization called FATE and trained to be a human weapon. Now, four years later, she receives her assignment: protect Gareth


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Interventional Cardiology Symposium
We thank attendees of the Geoffrey O. Hartzler Interventional Cardiology Symposium 2016. The 2016 Symposium was held at the Grand Wailea Resort, Maui, Hawaii from 11-13 July 2016. Attendees enjoyed a refreshed program based on the theme of Excellence in Intervention through Interaction.
Our sincere thanks to William O'Neill who delivered our keynote address, the Geoffrey O. Hartzler Memorial Lecture. We also acknowledge the Symposium faculty from the United States, Australia, New Zealand and Asia. Sign up for updates so you receive the latest information on the 2017 Symposium.
Symposium Directors
J. Aaron Grantham, MD
Saint Luke's Mid America Heart Institute
Kansas City, Missouri, USA
Rajiv Gulati, MD, PhD
Mayo Clinic
Rochester, Minnesota, USA
Steven P. Marso, MD
University of Texas Southwestern
Dallas, Texas, USA
Barry D. Rutherford, MD
Saint Luke's Mid America Heart Institute
Kansas City, Missouri, USA
Stephen G. Worthley, MBBS, PhD
Royal Adelaide Hospital
Adelaide, Australia


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Superhydrophobic Materials: Peanut Leaf Inspired Multifunctional Surfaces (Small 2/2014)
After millions of years of evolution, the peanut leaf could collect water from the foggy atmosphere to perfectly survive and adapt to the arid environment owing to its special structure and wettability. The peanut leaf shows high-adhesive superhydrophobicity, arising from the formation of the quasi-continuous and discontinuous three-phase contact line on the microscale and nanoscale. Furthermore, this highly-adhesive and superhydrophobic peanut leaf is proved to be efficient in fog capture. Inspired by the peanut leaf, K. Liu and co-workers report on page 294 the preparation of multifunctional surfaces with structural similarity to the natural peanut leaf, which exhibit simultaneous superhydrophobicity and high adhesion towards water.


text: Home Recipes Ingredients Chocolate Recipes Chocolate Desserts Share: Chocolate Desserts What could be better than chocolate for dessert? From chocolate dessert cups, cakes, pudding, and bars, these tasty chocolate desserts are sure to please. Recipe Spotlight Sue's Chocolate Zucchini Cake Sue Falk Our family absolutely loves zucchini, especially when we grow it ourselves. We've found many ways to use it, including this spiced cake that's super moist and chocolaty good. —Sue Falk, Warren, Michigan Get Recipe More Chocolate Desserts Previous Page ... 4 5 6 ... 174 Next Page Lovelight Chocolate Cake Lovelight Chocolate Cake —Eilene Bogar, Minier, Illinois View Recipe Low-Fat Chocolate Sauce Low-Fat Chocolate Sauce Unlikely most delicious desserts, this creamy sauce contains just a trace of fat. So I can satisfy my sweet tooth with little guilt.—Beverly Irick, Indianapolis, Indiana View Recipe Mini-Choco Cupcakes Mini-Choco Cupcakes Cupcakes should be more than just cake batter divided into muffin tins. True cupcakes are not as crumbly as cake, but have a lighter texture than muffins.—Anette Stevens, Olds, Alberta View Recipe Advertise with us ADVERTISEMENT Peanut Butter Chocolate Chip Cookies Peanut Butter Chocolate Chip Cookies "With just four ingredients, this recipe couldn't be easier," comments Jeane Squires of Houston, Texas. "These moist cookies have a rich peanut flavor." View Recipe Sugar-Free Chocolate Fudge Sugar-Free Chocolate Fudge "I am borderline diabetic," relates Kaye Hartley of Jacksonville, Florida. "This fudge appeases my sweet tooth." View Recipe Three-Chocolate Fudge Three-Chocolate Fudge I make this fudge at Christmastime to give to friends and neighbors. That tradition started years ago when I made more candy than my husband, three sons and I could eat, so we shared it. It's a tasty tradition I'm glad to continue. -Betty Grantham, Hanceville, Alabama View Recipe Chocolate Walnut Squares Chocolate Walnut Squares Rich and satisfying, these bars create a symphony of flavors with every bite. The nutty crust, exquisite chocolate layer and the creamy frosting make this dessert one of my personal favorites. It's fun to take these treats to a potluck. —Anne Heinonen, Howell, Michigan View Recipe Sandy's Chocolate Cake Sandy's Chocolate Cake Years ago, I drove 4-1/2 hours to a cake contest, holding my entry on my lap the whole way. But it paid off. One bite and you'll see why this velvety beauty won first prize. —Sandra Johnson, Tioga, Pennsylvania View Recipe Soda Cracker Chocolate Candy Soda Cracker Chocolate Candy "My husband and I make several batches of this easy, chocolaty nut squares for holiday gifts," notes Margery Bryan of Royal City, Washington. "Most people are surprised to learn the recipe includes soda crackers." Married for 22 years, the couple recently retired and sold their ranch. Both love to cook. View Recipe Double Chocolate Chip Cookies Double Chocolate Chip Cookies "Who doesn't like chocolate chip cookies?" inquires field editor Diane Hixon, who credits cocoa in the batter for the double dose of chocolate in her treats. These disappear fast from the cookie jar in her Niceville, Florida home! View Recipe Chocolate Potato Cake Chocolate Potato Cake This secret ingredient in this moist rich chocolate cake is potatoes. It's a wonderful cake to make for a special occasion. The white fluffy frosting goes perfectly with the dark chocolate cake. —Jill Kinder, Richlands, Virginia View Recipe Previous Page ... 4 5 6 ... 174 Next Page Advertise with us ADVERTISEMENT Advertise with us ADVERTISEMENT


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Leaving Forch, ride through Rütihof and Hof and past the church in Wetzwil. Here the route climbs steadily, with a good view of Lake Zurich and the Albis, and passes through Toffwil to the highest point of the pass in Vorderen Pfannenstiel. If you want to get a unique panoramic view, climb up on foot to the Hochwacht and up the Bachtel tower. Thereafter comes a long downhill ride with romantic stretches and a marvelous viewpoint with an outdoor fireplace when you leave the woods on the Pfannenstiel – perfect for relaxing a while. Perhaps you have brought sausages and beverages in your backpack? Once refreshed, continue to Chrüzlen, finding quiet spots and idyllic ponds along the way. Meadows and fields lie to both sides as you proceed on to Willikon, where you can make a worthwhile side trip to the historic little town of Grüningen. The route to Lützelsee passes through marshland, interesting to those interested in natural protection, and the Lutiker Ried, arriving at one of the most attractive bathing beaches of the canton, on the Lützelsee. Ride through the charming tiny village of the same name with its magnificent half-timbered houses, and then continue on to Rapperswil, where you can end the trip with a boat ride on Lake Zurich.
Alternative A: Climb on foot from Vorderen Pfannenstiel to Hochwacht (ca. 0.6 km).
Alternative B: From Willikon to Grüningen (ca. 4 km).
The route is marked with «Radroute Zürichsee».
Places along the route: Forch - Wetzwil - Vorderer Pfannenstiel - Chrüzlen - Willikon - Lützelsee - Wolfhausen - Rapperswil
First published: Freitag, 29. Februar 2008
Last updated: Mittwoch, 15. Januar 2014


text: hi folks, running from one traditional xine problem to the next ;-} this time all the functions returning char ** pointers are causing trouble - their static memory model was nice, but with the new, dynamic multi-instance api i don't think they're really appropriate any more. *sigh* how about using xine_list_t* for this one (thus making xine_list public and addign a dispose function here) ? i think i better go to bed now, feeling really strange - hope i'll not dream of those malloc()s 8-} guenter -- "The other day I put instant coffee in my microwave oven ... I almost went back in time." -- Steven Wright