text: United States Patent: 7232474 ( 1 of 1 ) United States Patent 7,232,474 Bouvrette , et al. June 19, 2007 Process for producing gold nanoparticles Abstract Gold nanoparticles having a particle size of 4-15 nM are synthesized by the reduction of hydrogen tetrachloroaurate (III) trihydrate using a suitable reducing agent such as sodium citrate in the presence of unmodified .alpha., .beta. or .gamma.-cyclodextrin. The particle size is dependent upon the type and concentration of cyclodextrin and the reducing agent concentration. Gold nanoparticles having a particle size of 2-4 nM are produced by the reduction of hydrogen tetrachloroaurate (III) trihydrate using sodium borohydride in the presence of cyclodextrins. Inventors: Bouvrette; Pierre (Montreal, CA), Liu; Yali (Montreal, CA), Luong; John H. T. (Montreal, CA), Male; Keith B. (Montreal, CA) Assignee: National Research Council of Canada (Ottawa, CA) Appl. No.: 10/886,627 Filed: July 9, 2004 Current U.S. Class: 75/362 ; 75/371; 977/777 Current International Class: B22F 9/24 (20060101) Field of Search: 75/362,371 References Cited [Referenced By] U.S. Patent Documents 6025202 February 2000 Natan 6361944 March 2002 Mirkin et al. 2002/0177143 November 2002 Mirkin et al. 2003/0108612 June 2003 Xu et al. Other References Michels, Jasper J. et al., "Dendrimer-cyclodextrin assemblies as stabilizers for gold and platinum nanoparticles", J. Chem. Soc., Perkin Trans. 2, pp. 102-105, published Nov. 19, 2001. cited by examiner. Primary Examiner: Wyszomierski; George Attorney, Agent or Firm: Seaby; George A. Claims We claim: 1. A process for producing gold nanoparticles comprising the step of reducing hydrogen tetrachloroaurate (III) trihydrate with a reducing agent in the presence of an unmodified .alpha., .beta. or .gamma.-cyclodextrin, wherein the .alpha. or .gamma.-cyclodextrin is employed in a concentration of 25-50 mM to control particle size of the gold nanoparticles to 4.8 .+-.1.2 nm for .alpha.-cyclodextrin or 4.3 .+-.1.7 nm for .gamma.-cyclodextrin, or the .beta.-cyclodextrin is employed in a concentration of 15 mM to control particle size of the gold nanoparticles to within a range of 4.6-6.1 nm. 2. The process of claim 1, wherein the reducing agent is selected from the group consisting of sodium citrate and sodium borohydride. 3. The process of claim 1, wherein hydrogen tetrachloroaurate III trihydrate is dissolved in water to produce a solution; an unmodified .alpha., .beta. or .gamma.-cyclodextrin powder is added to the solution; the solution is heated to boiling; and sodium citrate is rapidly added to the solution while refluxing. 4. The process of claim 1, wherein sodium borohydride is added to a slowly mixing solution of hydrogen tetrachloroaurate III trihydrate containing an unmodified .alpha., .beta. or .gamma.-cyclodextrin. 5. The process of claim 1, wherein the particle size is further controlled by the concentration of the reducing agent. Description BACKGROUND OF THE INVENTION Field of the Invention This invention relates to a process for producing gold nanoparticles. Nanomaterials with size-dependent physical properties provide a plethora of opportunities for diversified and novel applications. In particular, gold nanoparticles are very attractive for research in nanotechnology because of their appealing features. For example, TiO.sub.2-supported gold nanoparticles display highly selective catalytic activity for CO oxidation at -70.degree. C. [M. Haruta, Catalysis Today 1997, 36, 153], while particles with diameters of 3-5 nm show a drastic decrease of the melting point. [Ph. Buffat et al, Phys. Rev. 1976, A13, 2287]. Moreover, non-toxic gold colloids, readily and inexpensively prepared by chemical reduction of HAuCl.sub.4, are capable of forming active complexes with many biological substances. [G. B. Birrell et al, J. Histochem. Cytochem. 1987, 35, 843]. Depending on the reducing agent employed, the particle size of the colloids can vary from 1-100 nm. [D. E. Handley In Colloidal Gold--Principles, Methods, and Applications; Hayat, M. A., Ed.; Academic Press: New York, 1989; Vol 1, Chapter 2, pp 13-32]: The sodium citrate reduction procedure pioneered by G. Frens [Nature Phys. Sci. 1973, 241, 20] is one of the most commonly cited methods for colloidal gold synthesis to produce nanoparticles with sizes of 12-64 nm, depending upon the citrate/HAuCl.sub.4 ratio. In immunocytochemistry, the use of smaller gold particles is preferred since steric hindrances are often encountered with larger particles, which can significantly reduce the number of sites for labeling. [G. B. Birrell et al, supra]. These small-diameter particles (3-6 nm) are often made using white phosphorus, sodium borohydride or a mixture of trisodium citrate and tannic acid as reducing agents [D. E. Handley, supra]. It is also of importance to be able to prepare monodispersed nanoparticles with a very narrow size distribution to exploit the size and quantum confinement effects of nanoparticles and to tailor nanomaterials with new properties. The nanostructure of Au or Ag films have been characterized by a wide range of analytical techniques including atomic force microscopy (AFM) [R. B. G. de Hollander et al Ultramicroscopy 1995, 57, 263] field emission scanning electron microscopy (FE-SEM) [M. Naitoh et al Jpn. J. Appl. Phys. 1992, 31, 4018], transmission electron microscopy (TEM) [W. J. Krakow Appl. Phys. 1990, 69, 2206; C. A. Davis et al, Opt. Commun. 1991, 85,70; M. Arai et al, J. Colloid Interface Sci. 1994, 168, 473; and S. Blacher et al J. Appl. Phys. 1993, 74, 207], near-field scanning optical microscopy (NSOM) [U. C. Fischer J. Opt. Soc. Am. B. 1986, 3, 1239], scanning tunneling microscopy (STM) [M. Rucker et al J. Appl. Phys. 1992, 72, 5027] and photon STM [P. Dawson Phys. Rev. Lett. 1994, 72, 2927]. Gold nanoparticles have been studied by AFM [R. H. Terrill et al J. Am. Chem. Soc. 1995, 1117, 12537 and W.-L Shaiu et al J. Vac. Sci. Technol. A 1993, 11, 820], TEM [M. Giersig et al Langmuir 1993, 9, 3408 and G. Chumanov et al J. Phys. Chem. 1995, 99, 9466], and SEM [I. G. Casella et al Analyst 1996, 121, 249 and A. Doron et al Langmuir 1995, 11, 1313] for the characterization of gold colloid monolayers. A recent comparison of four techniques, AFM, FE-SEM, TEM, and NSOM concludes that a combination of at least one scanning probe method (AFM, NSOM) and one accelerated-electron method (TEM, FE-SEM) is required to obtain the most accurate information regarding the nanometer-scale architecture of the particle-based surfaces. [K. C. Graber et al Anal Chem. 1997, 69, 471]. Sample preparation is also a key and crucial factor for obtaining good AFM imaging. The formation of self-assembled monolayers (SAMs) on various surfaces such as glass [J. H. Fendler Chem. Mater. 2001, 13, 3196], silicon [Z. Tang et al Langmuir 2002, 18, 7035 and D. Li et al J. Am. Chem. Soc. 1998, 120, 8797] and gold [H. X. Xe et al Langmuir 2000, 16, 3846] has been previously examined. In these procedures, the SAMs were prepared using compounds and polymers such as polyethylenimine (PEI), (3-aminopropyl)triethoxysilane (APTES), poly(diallyldimethylammonium) chloride (PDDA), poly(dimethyl)siloxane (PDMS), and n-octadecyltrichlorosilane (OTS) and alkanethiols. PDDA-modified silicon substrates have shown a distinct advantage over PEI and APTES modified substrates with respect to their very low surface roughness and surface height difference [Z. Tang et al, supra]. The roughness and largest surface height difference for the PDDA-modified silicon is 0.10 nm and 0.4 nm, while the corresponding values for PEI are 0.14 nm and 0.6 nm and for APTES 0.29 nm and 1.0 nm. In such preparation, CdSe/CdS colloids are absorbed on PDDA-modified silicon to form a homogeneous close-packed monolayer with little aggregation or multi-layer formation. Molecular self-assembly that exploits charge attraction between oppositely charged materials such as positively charged PDDA and negatively charged nickel phthalocyanine (NiPc), [D. Li et al, supra], cobalt phthalocyanine tetrasulfonate (Co.sup.IIPcTS.sup.4-) [Y. M. Lvov et al, J. Colloid Interface Sci. 1999, 212, 570] 1:12 molybdosilicate acid (SiMo.sub.12) [L. Li et al Mater. Chem. Phys. 2001, 69, 45] have been used to successfully fabricate multi-layered structures in a layer-by-layer manner on gold electrodes. Therefore, for the immobilization of small gold nanoparticles, PDDA could be the best candidate for SAM formation on the glass slide substrate to be used in conjunction with AFM measurements. Cyclodextrins (CDs) and modified cyclodextrins have been chemisorbed onto gold electrodes[M. T. Rojas et al J. Am. Chem. Soc. 1995, 117, 336; P. He et al Anal. Chim. Acta. 1997, 337, 217 and I. Suzuki et al Mater. Sci. Eng. C. 2001, 17, 149], gold films [M. Weisser et al Sens. Actuators. B. 1997, 38/39, 58 and D. Velic et al J. Mol. Struct. 2001, 598, 49], gold-coated AFM cantilevers [C. A. Tipple et al J. Anal. Chem. 2002, 74, 3118] and gold electrodes of a quartz microbalance [S.-C. Ng et al Tetrahedron Lett. 2002, 43, 2863] to exploit the host-guest interactions of cyclodextrins with solution partners. Per-6-thio-.beta.-CD [J. Liu et al J. Am. Chem. Soc. 1999, 121, 4304] and mono-6-lipoyl-amido-2,3,6-O-permethyl-.beta.-CD [T. Carofiglio et al Tetrahedron Lett. 2001, 42, 5241] have been added directly to gold nanoparticle solutions to form cyclodextrin-modified gold nanospheres. Recently, perthiolated cyclodextrins have been used to modify gold nanospheres by their addition directly to the gold solution during its reduction [J. Liu et al J. Am. Chem. Soc. 2001, 123, 11148 and J. Liu et al, Langmuir 2000, 16, 3000]. In these studies, HAuCl.sub.4 was reduced by sodium borohydride in the presence of perthiolated CDs in a solvent (either DMSO or dimethylformamide) milieu. The CDs bind directly to the gold surface through the SH functionality and the size of the gold nanoparticles formed was dependent upon the concentration and type (.alpha.,.beta., or .gamma.) of CD employed. The smallest particles were formed with .gamma.-SH-CD followed by .beta.-SH-CD and .alpha.-SH-CD, while increasing the ratio of CD/AuCl.sub.4.sup.- decreased the particle size. In spite of the advances outlined above, there are still problems encountered in the preparation of stable gold nanoparticles. In some cases, the chemicals used to stabilize the nano'particles may not be compatible with the desired applications for the particles. Moreover, the control of the size and distribution of nanoparticles is of concern, since smaller particles (less than 10 nm) are known to have improved electrochemical properties and greater sensitivity and resolution with respect to labeling procedures. However, smaller particles tend to be more unstable and easily undergo aggregation. Many of the aforementioned procedures for the preparation of smaller gold nanopaticles result in unstable colloids which rapidly aggregate and are not very useful for various applications. Although successful, many of the stabilization procedures for gold nanoparticles lead to colloid solutions which may not be very useful for chemical modifications and sensing applications due to both ionic repulsion and the known denaturing effects with respect to enzymes and proteins of surfactants such as SDS. SUMMARY OF THE INVENTION The object of the present invention is to provide a process for producing gold nanoparticles which results in relatively stable nanoparticles and which makes it possible to control the size and distribution of produced nanoparticles. Accordingly the invention relates to a process for producing gold nanoparticles comprising the step of reducing hydrogen tetrachloroaurate (III) trihydrate with a reducing agent in the presence of an .alpha., .beta. or .gamma.-cyclodextrin BRIEF DESCRIPTION OF THE DRAWINGS This invention is described below with reference to the accompanying drawings, wherein: FIGS. 1 and 2 are atomic force microscopy micrographs of gold nanoparticles at various dilutions made before immobilization at phase image-x,y scale of 1 .mu.m; FIG. 3 shows three graphs illustrating the effect of concentration on the size of gold nanoparticles; FIGS. 4A and 4B are transmission electron microscopy micrographs of gold nanoparticles; FIG. 5 is a graph illustrating the effect of the concentration ratio of sodium citrate/HAuCl.sub.4 on the size of gold nanoparticles as determined by AFM; FIG. 6 shows FT-IR spectra of 25 mM .alpha.-CD (solid line); and gold nanoparticles in the presence of 25 mM .alpha.-CD (closed circle, 20% of data); FIG. 7 shows FT-Raman spectra of 15 mM .beta.-CD (solid line) and 15 mM .beta.-CD with gold nanoparticles (closed circle, 10% of data); FIG. 8(A) shows an AFM micrograph of gold nanoparticles diluted 100-fold; height image-x,y-scale of 5 .mu.m and section analysis and (B) an AFM micrograph of gold nanoparticles diluted 200-fold; height image-2,y-scale of 5 .mu.m and section analysis; and FIG. 9 shows TEM micrographs of gold nanoparticles taken at 200 kV. DETAILED DESCRIPTION OF THE INVENTION Preparation of Gold Nanoparticles Glassware was cleaned in aqua regia (nitric acid/hydrochloric acid: 1/3) and all solutions were prepared using Milli Q (Millipore, Bedford, Mass.) A-10 gradient (18 M.OMEGA. cm) deionized water. The reaction (100 mL final volume) was performed in a 3-neck 500 mL round bottom flask with the center neck attached to a reflux condenser. The flask was set in a heating mantle with a magnetic stirrer to provide continuous mixing. Gold nanoparticles were prepared by the method of Storhoff et al [J. J. Storhoffet al J. Am. Chem. Soc. 1998, 120, 1959] with slight modifications. A 20 mL solution of 5 mM hydrogen tetrachloroaurate (III) trihydrate (99.9%, Aldrich, Milwaukee, Wis.) was added to the flask and the volume was made up to 90 mL with water. Cyclodextrin powders were added to the flask through one of the open necks to obtain final concentrations: 1-25 mM for .beta.-cyclodextrin hydrate (Aldrich, MW, 1135), 5-50 mM for both .alpha.-cyclodextrin (Aldrich, MW, 972) and .gamma.-cyclodextrin (Wacker Chemicals, Norwalk, Conn., MW, 1297). The resulting solution was heated until boiling and then 10 mL of 40 mM sodium citrate were rapidly added to the flask. The solution changed color rapidly (10-40 s) from clear to a murky gray color indicating nucleation. Within 2 min the color changed to burgundy red, an indication of gold nanoparticle formation. The solution was allowed to reflux for a further 15 min and then was cooled to room temperature. Solutions were filtered (0.45 .mu.m filters, Millipore) and stored at 4.degree. C. This procedure was essentially the same as the commonly cited method of Frens [supra] except that the starting concentrations of gold and sodium citrate are 4.0 and 3.3-fold higher, respectively. The concentration of sodium citrate was also altered to evaluate its effect on the gold nanoparticle size. Gold nanoparticles were also prepared by the reduction of hydrogen tetrachloroaurate (III) trihydrate with sodium borohydride by the method of Birrell et al [supra] with minor modifications. In brief, 0.25 mM HAuCl.sub.4 (50 mL) was prepared and then 100 .mu.L aliquots of freshly prepared 0.1 M sodium borohydride (NaBH.sub.4) were added at 22.degree. C. to the slowly mixing solution of gold until a stable orange colored colloid was observed (.apprxeq.0.8-1.2 mL NaBH.sub.4). The reaction was left for 18 hr at 22.degree. C. and finally, solutions were filtered as described earlier and stored at 4.degree. C. The nanoparticles were also prepared in the presence of 10 mM .alpha.-CD, .beta.-CD or .gamma.-CD in the hydrogen tetrachloroaurate (III) trihydrate solution. All chemicals were of analytical reagent grade and used as received without any further purification. Immobilization of Gold Nanoparticles on Modified Glass Surface Glass microscope slides (25.times.75.times.1 mm, Fisher, Fair Lawn, N.J., Cat# 12-552) were cut into smaller pieces (25.times.10 mm) and carefully cleaned by soaking in a solution of nitric acid/water (50/50%) for 20 min. Rinsed slides were immersed in Piranha solution (70% concentrated sulfuric acid: 30% hydrogen peroxide, 7:3) for 20 min and extensively rinsed with water. Cleaned glass slides were dried under a nitrogen stream and immersed in 0.01 M poly(diallyldimethylammonium chloride), (PDDA, MW 200,000-350,000, Aldrich) for 16 h. The concentration was based on the monomer molecular weight of 161 and takes into account that the polymer solution was only 20%, i.e., 0.161 g of polymer was used to prepare a 20 mL solution. The resulting glass slides were thoroughly rinsed with deionized water and dried under a nitrogen stream. The polymer-coated slides were subsequently incubated for 2-3 h with the gold nanoparticle solutions described above. In order to obtain AFM images with homogeneously dispersed gold nanoparticles the solutions were diluted 50- to 200-fold, depending upon the cyclodextrin concentration in the sample. Measurements and Characterization UV-vis spectroscopy measurements (300-800 nm) were performed using a Beckman spectrophotometer (DU-640, Fullerton, Calif.) at room temperature with a 1-cm optical, length cuvette. Gold nanoparticle solutions prepared above were diluted 5-fold before measurement and their stabilities were monitored with time under various conditions. AFM images were obtained using a Nanoscope IV (Nanoscope IV, Digital Instruments-Veeco, Santa Barbara, Calif.) with a silicon tip operated in tapping mode to characterize the various gold nanoparticle preparations. The mean particle size and standard deviation was then calculated for each sample. The images obtained by AFM were not manipulated, altered or enhanced in any way. A transmission electron microscope (TEM Philips CM20, Philips, FEI, Hillsboro, Oreg.) equipped with a Gatan UltraScan CCD camera was used for gold nanoparticle characterization. Images were taken under 200 kV and TEM resolution can be achieved to 0.25 nm. A few drops of sample solution-were placed on a 300 mesh carbon-coated copper grid with holey carbon film and dried at room temperature before TEM examination. For each TEM image, the mean particle size and standard deviation was calculated from either the particle area or perimeter/length mode using Scion Image (Scion Corp., Frederick, Md.) based on the popular NIH Image on the MacIntosh platform. For each sample, analysis was performed on four (gold nanoparticles formed by sodium citrate reduction) or two (gold nanoparticles formed by sodium borohydride reduction) TEM images of various sizes such that between 30-350 particles could be observed. Solution phase FT-Raman spectra were recorded using a Bruker FRA 106 spectrometer (Bruker Optics, Milton, ON, Canada) equipped with a liquid nitrogen-cooled germanium detector and a 1064 nm Nd:YAG laser. Samples were mounted inside the instrument using a 0.5 cm quartz cuvette with a mirrored rear surface. The Raman spectrum was collected within the 0-4000 cm.sup.-1 interval with 4 cm.sup.-1 resolution using 500 mW of excitation laser power. Solution phase FT-IR spectra were recorded using an ASI Applied Systems (Mettler-Toledo company) ReactIR-4000 spectrometer (Millersville, Md.) equipped with a purge gas generator from Parker Balston (Haverhill, Mass.). The Ft-IR spectrum was collected within the 600-4000 cm.sup.-1 interval. The CD-gold colloids were examined by a triple quadrople mass spectrometer (API III LC/MS/MS, Sciex, Thornhill, ON, Canada) to monitor the possible degradation or modification of CD during the course of the citrate reduction of hydrogen tetrachloroaurate (III) trihydrate. Ammonated species of CD were generated by spraying the sample solution (ammonium acetate in methanol) through a stainless steel capillary held at 4-6 kV. The sample solution was delivered to the sprayer by a syringe infusion pump through a fused silica capillary of 100 .mu.m I.D. at 1 .mu.L/min. A gas curtain formed by a continuous flow (0.6-0.8 L/min) of N.sub.2 in the interface region served to evaporate the aerosol droplets and to break up the cluster formation from supersonic expansion. The potential on the sampling orifice of the instrument was set at +50 V. Characterization of Gold Nanoparticles by UV-vis Spectroscopy Gold nanoparticles formed by the reduction of hydrogen tetrachloroaurate (III) trihydrate with sodium citrate exhibited a red color and upon dilution (5-fold) revealed a strong absorption (0.6-0.7) with the characteristic peak at 518-520 nm. The addition of cyclodextrins at high concentration (>15 mM) to the reaction mixture resulted in a slight shift to shorter wavelengths (516-518 nm), an indication of a decrease in the gold nanoparticle diameter size. However, in the presence of 15 mM .beta.-CD, decreasing the concentration of sodium citrate (0.33-0.50 fold) added to the reaction mixture resulted in a shift to longer wavelengths (522-534 nm), indicating an increase in the gold nanoparticle diameter size. The times until nucleation and the red color development were faster (10 and 45 s, respectively) in the presence of cyclodextrins compared to in the absence of cyclodextrins (40 and 90 s, respectively). The sample solutions (diluted five-fold) were monitored with time at room temperature, 4.degree. C., in the dark, plus and minus cyclodextrins. Samples left at 4.degree. C. were more stable than those at room temperature whereby precipitation was often observed. Sample storage in the dark exhibited no effect on the nanoparticle stability. Samples at 4.degree. C. containing cyclodextrins were stable for at least 3 months whereas the sample without cyclodextrin lost 10-15% of its initial absorbance during the same time period. The stock sample of gold nanoparticles with 25 mM .beta.-CD was not stable at 4.degree. C. due to the insolubility of the cyclodextrin upon cooling. Gold nanoparticle stock solutions with 15 mM .beta.-CD and citrate: Au ratios less than 1.3:1 also precipitated. Gold nanoparticles formed by the reduction of hydrogen tetrachloroaurate (III) trihydrate with sodium borohydride were also red in color and revealed a strong absorption (0.6-0.7) with the characteristic peak at 515-517 nm. The addition of cyclodextrins (10 mM) to the reaction mixture resulted in a shift to shorter wavelengths (510-512 nm), indicating a decrease in the gold nanoparticle diameter size. Characterization of Gold Nanoparticles by AFM Gold nanoparticles prepared by sodium citrate reduction in the absence of cyclodextrins, were immobilized on PDDA treated glass slides and analyzed with AFM. A nanoparticle monolayer was formed on the PDDA polymer after just 2-3 hours with a surface roughness of 3.8 nm, indicating a very uniform layer. However, once the sample was diluted 4-fold, as shown in FIG. 1, a nanoparticle semi-mono layer (11, 9 nm) was observed after 2-3 hours. The gold nanoparticles formed a very homogeneous close-packed semi-monolayer with little aggregation or multi-layer formation. As shown in FIG. 2, excellent gold nanoparticle dispersion was observed (FIG. 3) when the sample was diluted 50-fold and thus height analysis could easily be performed. The particle size for this image was determined to be 11.9.+-.1.7 nm (n=994) and the largest surface height difference for the PDDA-modified glass (section with no gold nanoparticles) was about 0.8 nm which was similar to the value reported for PDDA-modified silicon [Z. Tang et al, supra] The average particle size obtained for three different samples ranged between 12-15 nm with an average of 13.3 nm. As predicted from UV-vis measurements, the size of the gold nanoparticles decreased as the concentration of .beta.-CD increased. The smallest particles were obtained at 15 mM .beta.-CD and the average particle size obtained from three different samples ranged between 4.6 and 6.1 nm with an average of 5.4 nm. A sample diluted 200 fold and left refrigerated at 4.degree. for three months was reanalyzed by AFM as shown in FIG. 2B. The particle size remained virtually unchanged (5.9.+-.1.4, n=2593) with insignificant aggregation, indicating very good stability of the gold nanoparticles in the presence of cyclodextrin. FIG. 3 illustrates the effect of the concentration of the three cyclodextrins on the particle size. As observed, gold nanoparticle size was also reduced upon the addition of .alpha.-CD and .gamma.-CD. However, the smallest particles were observed at CD concentration of 25-50 mM rather than 15 mM, as was the case with .beta.-CD. The smallest particle sizes were 4.8.+-.1.2 nm (n=889) and 4.3.+-.1.7 nm (n=1278) for .alpha.-CD and .gamma.-CD, respectively. Since the CDs would exhibit hydrophobic interactions with embryonic gold nanoparticles [A. V. Kabashin et al J. Phys. Chem. B 2003, 107, 4527], the consecutive particle growth due to the mutual coalescence between such nanoclusters would be severely limited or terminated as the CD concentration increased. The gold nanoparticle solutions in the presence of CDs were diluted 200-fold instead of only 50-fold to obtain a good dispersion of particles. Since the immobilization procedure with PDDA modified glass was dependent upon the starting particle concentration, the solutions with smaller gold nanoparticles produced in the presence of CDs would have to be diluted more to attain a similar particle density. Undiluted gold nanoparticles (prepared in the presence of 15 mM .beta.-CD) immobilized on PDDA-modified glass also formed a very uniform monolayer after 2-3 h. The surface roughness was just 2.4 nm compared to the value of 3.8 nm observed in the absence of CDs, and this difference was likely due to the smaller particle size. Characterization of Gold Nanoparticles by TEM TEM micrographs taken at 200 kV of gold nanoparticles in the absence of cyclodextrin (FIG. 4A) and in the presence of 25 mM .alpha.-CD (FIG. 4B) show the homogeneity of the samples as well as the expected spherical shape of the small gold nanoparticles. The average size of gold nanoparticle in the absence of cyclodextrins (four different images) was determined to be 14.4.+-.1.2 nm (n=177), which matched well with the value (13.3 nm) determined by AFM. The average particle sizes in the presence of 25 mM .alpha.-CD, 15 nM .beta.-CD and 25 mM .gamma.-CD (four different images) were 6.7.+-.1.0 nm (n=715), 6.6.+-.1.2 nm (n=831), and 6.0.+-.1.3 nm (n=370), respectively, which also agreed well with the corresponding AFM results of 5.8, 5.4 and 4.3 nm. As shown in FIG. 5, altering the concentration ratio of sodium citrate to tetrachloroaurate used for the reduction reaction also changed the particle size. In the presence of 15 mM .beta.-CD the particle size increased from 5.4 nm to 25.0.+-.6.9 nm (n=827) as the concentration ratio of citrate:gold was decreased 3-fold from 4:1 to 1.3:1. However, increasing the sodium citrate:gold concentration ratio from 4:1 to 6:1 exhibited insignificant effect on the size. Similar effects of the sodium citrate to gold concentration ratio on gold nanoparticle size have been reported previously by Frens [supra]. At ratios of citrate:gold less than 1.3:1, the solutions became murky an indication that as the gold nanoparticle size became larger, i.e. the particle density was too high for the particles to remain soluble in solution. At a ratio of 1:1 the particle size seemed to be in the range of 40-50 nm, but the analysis was not very reliable because the particle size distribution was quite large (.+-.15 nm). Reducing the concentration of the components of the reduction reaction four-fold (gold 0.25 mM, citrate 1.0 mM) exhibited no impact on the size of the particles, i.e., only the ratio of the components was critical in determining the size of gold nanoparticles. Similarly, if the concentration of the .beta.-CD was also reduced from 15 mM to 3.75 mM, the particle size was not altered, indicating that the ratio of .beta.-CD to gold was critical, not the absolute .beta.-CD concentration. Fate of the Cyclodextrins FT-Raman, FT-IR spectroscopy, and mass spectrometry were used to follow the role of the cyclodextrins during the reduction of tetrachloroaurate by sodium citrate. Mass spectrometry data confirmed that the gold colloid samples prepared in .alpha., .beta. and .gamma.-CD, respectively still exhibited molecular masses corresponding to 972, 1135, and 1297, the molecular weight of the three CD molecules and there were no other peaks recorded. Consequently, CDs were considered intact during the course of the tetrachloroaurate reduction. FT-IR measurements were conducted to probe any possible gold-CD interactions. It should be noted that the spectra of gold nanoparticles alone was featureless and revealed only a flat baseline. The spectra of 14 mM .beta.-CD in the presence and absence of the gold nanoparticles were virtually identical (FIG. 6) and similar spectra were observed with .alpha.-CD and .gamma.-CD. Therefore, no evidence of Au--O interactions could be deducted from the FT-IR spectra. This point was taken into account since there are 18, 21 and 24 hydroxyl groups for .alpha.-CD, .beta.-CD and .gamma.-CD, respectively. [J. Szejti In Comprehensive Supramolecular Chemistry; Atwood, J. L.; Davies, J. E. D.; MacNicol, D. D.; Vogtle, F., Eds.; Permagon-Elsevier: New York, 1996; Vol 3, pp 5-40]. In the case of resorcinarenes which also stabilize gold nanoclusters, binding of the gold atoms by chemisorption through Au--O interactions was suggested from surface-enhanced Raman spectroscopy (SERS) [K. B. Stavens et al A Langmuir 1999, 15, 8337]. Therefore, FT-Raman measurements were taken in an attempt to probe the interaction between gold and the primary macrocyclic structure of the CDs as discussed below. CDs have been known to form inclusion complexes with various small hydrophobic molecules and the internal diameters of the apolar cavities of .alpha.-CD, .beta.-CD and .gamma.-CD are 570, 780, and 950 pm, respectively [Szejtli, supra]. With such dimensions, it would be possible for single hydrophobic gold atoms (288 pm in diameter) or small gold nanoclusters to be enclosed in the CD cavity to form an inclusion complex [Kabashin et al, supra]. Indeed, it has also been reported that the apolar rhodium nanoparticles [M. Komiyama et al Bull. Chem. Soc. Jpn 1983, 56, 2883] and Pd colloids [I. Willner J. Am. Chm. Soc. 1989, 111, 1330] are stabilized by hydrophobic cavities of a number of CDs and .beta.-CDs, respectively. Inclusion of gold atoms in the CD cavities would remove them as an available feedstock for nanoparticle growth, thus ultimately reducing the particle size. No reduction in the intensity of the low-frequency .beta.-CD modes corresponding to pyranose ring vibrations along the backbone of CD [Wiedenhof et al Die Starke 1969, 21, 119] was observed following the production of gold nanoparticles (FIG. 7). A dampening of these modes would suggest an interaction between gold and the primary macrocyclic structure of the CDs, suggesting that a small number of gold atoms could be held within the hydrophobic cavity of the CDs. This dampening effect was noted in the case of gold nanoparticles (2-2,4 nm) fabricated using femtosecond laser ablation in an aqueous solution of 10 mM .beta.-cyclodextrin [Kabashin et al, supra]. Since dampening was not observed with citrate reduction, it was unlikely that gold atoms were included in the CD cavities, implying that the rapid reduction of the tetrachloroaurate solution by sodium citrate prevented this inclusion complexation step. Therefore the reduction of the gold nanoparticle size in the presence of CDs was more likely attributed to the hydrophobic interactions between the hydrophobic cavity CDs and large gold nanoparticles rather than the inclusion of gold atoms or small gold nanoparticles in the CD cavities. Hydrophobic-hydrophobic interactions were responsible for the solubilization of very large polyaromatic hydrocarbons (PAHs) by various cyclodextrins [K. B. Male et al Enz. Microbial Tech. 1995, 17, 607]. These large molecules cannot fit into the hydrophobic cavities of the CDs because they have sizes incompatible with the dimensions of the cavity. However, they become soluble in CDs because a certain groups of side chains of such PAHs might be able to penetrate into the CD hydrophobic cavity to display hydrophobic interactions. Therefore, the inventors reason that the large gold nanoparticles obtained in this study cannot fit into the CD cavities but they can be situated on the top of the CD cavity to form another form of complexation. Due to such hydrophobic interactions with the CDs, gold nanoparticles are less likely to agglomerate with other nanoparticles which will result in a smaller particle size. The resulting nanoparticles were much smaller and more stable with an increase in the CD concentration implying that hydrophobic interactions between gold nanoparticles and CD molecules were of sufficient strength to prevent agglomeration. Very recently, surfactants such as resorcinarenes [Stavans et al supra] and SDS [F. Mafune et al J. Phys. Chem. B. 2001, 105, 5114] have been used to stabilize gold nanoclusters. The surface of gold nanoparticles would be completely covered by negatively charged SDS which renders such particles not as useful for chemical modifications or biosensing applications, due to both ionic repulsion and the known denaturing effects of SDS with respect to enzymes and proteins. Gold nanoparticles in the presence of neutral cyclodextrins are not subject to such shortcomings as encountered by SDS coated gold nanoparticles. Preparation of Gold Particles using Sodium Borohydride As shown in FIG. 8A, gold nanoparticles having a particle size of 6.0.+-.1.7 nm (n=1003) were formed by the reduction of hydrogen tetrachloroaurate (III) trihydrate with sodium borohydride. As illustrated in FIG. 8B, the addition of 10 mM .beta.-CD significantly reduced the particle size to 3.1.+-.0.9 nm (n=3161) and similar effects were seen with 10 mM .alpha.-CD (2.0.+-.0.9 nm, n=3702) and 10 mM .gamma.-CD (2.4.+-.0.8 nm, n=2699). The gold nanoparticle sizes determined in the presence of cyclodextrins were very close to the detection limit of the AFM technique, since the largest surface height difference for the PDDA substrate was determined to be 0.8 nm and these particles are in the range of 2.0-3.0 nm such that the S/N =3. Although the particle distribution curves have lost some of their Gaussian shape for the three cyclodextrin samples, no gold nanoparticles were observed above 4.0 nm. As clearly indicated from the TEM micrographs of the gold nanoparticles produced by sodium borohydride reduction in the absence of cyclodextrin (FIG. 9A) and in the presence of 10 mM .beta.-CD (FIG. 9B), reduction of gold solution by sodium borohydride in the presence of cyclodextrin reduced the gold nanoparticle size significantly. Two images were analyzed for each sample and the particle size was determined to be 7.4.+-.0.8 nm (n=94) in the absence of cyclodextrins. In the presence of 10 mM .alpha.-CD, .beta.-CD and .gamma.-CD, the particle sizes were, 3.7.+-.0.7 nm (n=80), 3.7.+-.0.8 nm (n=150) and 3.4.+-.0.9 nm (n=81), respectively. These results indicated that the presence of cyclodextrins during the reduction of hydrogen tetrachloroaurate (III) trihydrate reduced the gold nanoparticle size regardless of which reducing agent was used, sodium borohydride or sodium citrate. In summary, this invention is believed to be the first attempt to prepare gold nanoparticles by chemical reduction in the presence of unmodified cyclodextrins. On the basis of data obtained using UV-vis, FT-IR spectroscopy, mass spectrometry and FT-Raman spectroscopy, the formation of gold cluster-cyclodextrin inclusion complex is not evident. Cyclodextrins remain intact during the course of preparation and unlike resorcinarenes [Stavens et al, supra] there is no chemisorption between gold nanoparticles and cyclodextrins. Hydrophobic-hydrophobic interactions between cyclodextrins and gold nanoparticles are suggested as the main rationale behind the stabilization of gold colloids by cyclodextrins. * * * * *


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Brunei Postpones Death by Stoning Law
BY Michelle Garcia
April 23 2014 1:09 PM ET
The government of Brunei will postpone the implementation of a law that would allow a sentence of death by stoning for people found guilty of having gay sex, among other offenses including adultery, robbery, and defamation of the Prophet Muhammad.
Sharia law was scheduled to go into effect beginning Tuesday, but the government announced that implementation would be postponed due to "unavoidable circumstances," the The Wall Street Journal reports. Officials have not announced the new implementation date, but Jauyah Md. Zaini of the government's Islamic legal unit said the law would go into effect "in the very near future."
Earlier this month, the United Nations condemned the government for putting such sentencing in place, especially since the small Asian country ended the death penalty in 1957.
"Under international law, stoning people to death constitutes torture or other cruel, inhuman, or degrading treatment or punishment and is thus clearly prohibited," Rupert Colville, spokesman for the Office of the U.N. High Commissioner for Human Rights, said at a news conference in Geneva last week.
Colville said that in countries where death by stoning is allowed, it usually leads to more women receiving the sentence, so women, along with sexual minorities, would especially be targeted under the law.
Under Brunei's constitution, His Majesty Paduka Seri Baginda Sultan Haji Hassanal Bolkiah Mu'izzaddin Waddaulah leads all areas of government. The sultan is also the owner of the Beverly Hills Hotel, which has recently been the subject of a boycott in relation to Brunei's pending law.
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subset: commoncrawl


text:
AM Juster
Poems by AM Juster : 5 / 10
Long Strange Trip
The flower children gone to seed
Bake brownies for the PTA
And give to liberals in need.
Their ponytails display some gray
And nothing tie-dyed ever fits
Despite the tofu and sorbet.
Now they are mocked as "hippie-crits"
By free-range children who refuse
To heed their parents' tired views
On love and peace and endless summer.
What a bummer.
Submitted: Friday, January 03, 2003
Poems by AM Juster : 5 / 10
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Sony, YouTube to stream 'The Interview'
Person with knowledge of decision to AP: Josh Smith, released by Pistons,...
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Cartoonist and illustrator Patrick LaMontagne updates the mental image we...
OSHAWA -- Heading out to do their Christmas shopping, some Oshawa...
ST. PAUL, Alta. - The attention of an Alberta town shaken by a shootout and the death of a priest has now turned to a local businessman who managed a health and vitamin store.
RCMP said John Carlos Quadros, 55, of St. Paul died Friday evening during a gun battle in which three mounties were injured. It took place on the town's busiest street while residents fled for cover.
St. Paul Mayor Glenn Andersen said Quadros managed Health Mart 2000, which is located only a short distance from where the confrontation happened.
He said no one has an answer about what may have sparked Friday's rampage.
"It's a question that could be in everybody's minds forever — what was the stressor? What would provoke somebody to do something like this?" Andersen asked.
RCMP said they continued to investigate the slaying of Father Gilbert Dasna, 32, to try to determine whether his death is related to the confrontation with police.
St. Paul's downtown was bustling on Friday when the bizarre sequence of crimes began. Shops were closing, people were heading home from work and two nearby schools were hosting events.
Gunshots rang out near the town's RCMP detachment and police began hunting for a black pickup that was seen leaving the area. At about the same time police got a distress call from the rectory of a Catholic church. When they arrived, they found the priest dead.
The Diocese of St. Paul said Dasna was a native of Cameroon who had served the diocese since 2011.
Pierre Lamoureux, a spokesman for the diocese, said a church official was told that Dasna was discovered lying in the doorway of the rectory with what were believed to be gunshot wounds in his chest.
Police said the black truck later rammed a police vehicle in downtown St. Paul, pinning an officer inside. The shootout followed, and at the end, Quadros was dead.
The website for Health Mart 2000 lists John as a co-manager and says the business offers natural products, herbs, vitamins, organic foods, personal hygiene products as well as sport and bodybuilding supplements.
"At Health Mart 2000 we believe that the road to optimal health may be achieved thru a natural approach, using Herbs and Natural products given to us by GOD, as our inherent right as his adopted children; and a continued daily effort to know our Lord and saviour Jesus Christ, the way to Salvation and ever Lasting Life," the website states.
Andersen said he hadn't known Quadros personally, but that he had been a businessman in St. Paul for about 15 years and that he had no reason to think there was anything unusual about him.
At one point, Andersen said Quadros had spoken to council about a requirement concerning business licences. But he said there was nothing strange about the presentation.
Andersen said Quadros was married and lived above the store.
"Our community is a safe community and I believe this is an isolated incident," Andersen said.
The RCMP officer that was in the vehicle that was rammed suffered extensive injuries to both legs and was transported to hospital in Edmonton. Police said Saturday that her injuries were not life-threatening.
The two other officers, police said, were treated and released.
Alberta's Serious Incident Response Team, a provincial unit that investigates the use of force by police, has now taken over the probe into the gunfight.
Dasna's death, meanwhile, has hit the local Catholic community hard.
Lamoureux said he had no idea why anyone would kill the priest. He said it wasn't known if Quadros was a member of the church.
Funeral arrangements have not yet been made.
"We've lost a friend and a pastor and we're all suffering from that loss," Lamoureux said.
—By Rob Drinkwater in Edmonton
By The Canadian Press
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Here, you...


text:
Photo: A subterranean view of Chip and Dale's Nuthouse when it's not inundated in meaning
Nobody is sure what the target audience of Chip and Dale's Nuthouse is. It at one time had stuff to do, but Disney lawyers had it taken away to make it harder for kids to get exercise.
You shouldn't try Zombie Mode
© copyright 2011–2014
A Pants Aflame production


text:
Paris Hilton Releases Colorful Video for 'Come Alive' (Video)
Great news for anyone who regularly quotes "If you show me real love baby/ I'll show you mine": Paris Hilton has released a video for her new single "Come Alive," on Cash Money Records.
This article originally appeared on Billboard.com.
Never miss a story. Stay up-to-date with THR's Daily Headlines.
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text:
We're going to a wedding the first weekend in August where guests will be staying in the downtown Courtyard Marriott. Afterward we will continue north to go camping so we will have our 25' travel trailer with us. The Marriott told us we can park it in the Grand Avenue parking structure for $15 a day. We thought of parking in a Walmart but since we'd unhook our truck to drive in to the wedding that wouldn't be very safe to leave the trailer there. We'd rather find a campground to park and stay in and just drive in to the wedding in the city. I think that's also the state fair so maybe this isn't even possible. Does anyone have suggestions of campgrounds or other parking ideas? Thanks so much in advance!
Milwaukee RV parking by the downtown Courtyard Marriott or camping sites
3 Replies | Jump to last reply |
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You are right about State Fair--it's Aug 2-12.
I believe that Jellystone (in Caledonia) has RV camp sites.
When we attend a wedding, I like staying where the other guests are, and the $15 parking rate seems pretty reasonable.
Report Abuse
Hi - there isn't a Walmart close and the Grand Avenue parking structure fee is reasonable plus its nearby so you can check up on it regularly. The area could be a little sketch so I would recommend it. Jellystone is the closet official campground (not very close however) but the State Fairgrounds hosts RV's all year round so unless it changes during fair week I would check there first. Its closer than Jellystone - maybe 15-20 minutes west depending on traffic.
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Sounds like Jellystone is a little too far so will check out the fair but maybe the hotel and extra parking is the way we'll need to go. Thanks for the help!
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TULSA — Sometime after 9 p.m. Saturday night, Cowboys offensive coordinator Todd Monken helped himself to the snack line running behind the visiting coaches booth at H.A. Chapman Stadium.
OSU-Tulsa fiasco: Only folks in Hawaii could appreciate this kickoff time
A few chips, a dab of French onion dip, handful of popcorn.
And no, his offense wasn't in control against Tulsa, the game wasn't in hand, like Lafayette and Arizona were previously at that hour.
The game hadn't even started.
Lightning and the threat of high winds demanded a delay, which pushed kickoff toward normal curfew for the Cowboys.
Anybody still on board with scheduled 9 p.m. kickoffs in the central time zone?
So much for TV exposure, unless you're seriously trying to expand the brand, say, to Maui. So much for TU's big home game with the cross-state rival, and all the benefits it brings, as a line of taillights were spotted exiting campus before school officials even started talking about Plan B. Think folks might be asking for refunds on those $95 ducats – the most expensive single-game tickets in program history?
We're still seeking confirmation on the rumor that the Cowboys considered switching to a previously unknown 49th uniform combination: pajamas.
Way back when the time for kickoff was revealed, OSU coach Mike Gundy asked a handful of writers, "Who's responsible for that start time?"
TU, that's who.
Sure, weather happens. It's not TU's fault that a storm rolled in and lightning chased fans inside to the nearby Reynolds Center, where people joked of a "sold-out crowd."
It's already been a weird weather month, with a slew of games delayed, even big games like Notre Dame-South Florida and West Virginia-Marshall, which was eventually called in the fourth quarter. Saturday night in Waco, lightning caused a second-quarter delay and a decision to skip halftime and reduce the third and fourth quarters to 12 minutes. With the Bears rolling 48-0, the game was called after three quarters.
Continue reading this story on the...
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Photo Gallery
Terrorist who planted bomb on Honolulu flight to be released
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In this 1989 file photo Mohammed Rashed speaks during his trial in Athens, Greece, in connection with a fatal 1982 Pan Am 830 bombing. (AP Photo/File)
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Very great pick , Fun for the whole family. Great story , fun actors, highly recomend.
I really enjoyed this DVD. A person must watch The Chrismas Shoes first. I would encourage anyone to buy both. I was touched how someones lose of a loved one became happiness for another. The actors were excellent.
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Customer Reviews for
Autobiography of a Fat Bride: True Tales of a Pretend Adulthood
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Posted August 14, 2011
Complety unfunny. Waste of my time and money. I had to force myself to finish reading it just so that I feel I got my moneys worth. I though I was getting a lough out loud read but was greatly dissapointed and wondered what the hell other reviewers read cuz it wasnt this book.
0 out of 1 people found this review helpful.Was this review helpful? Yes NoThank you for your feedback. Report this reviewThank you, this review has been flagged.
Posted July 1, 2012
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Archive Page - 08/16/13 40 years, 2,169 covers and 54,876 stories from PEOPLE magazine's history for you to enjoy
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- April 25, 1983
- Vol. 19
- No. 16
David Hasselhoff Supercharges Knight Rider—but Sorry, Gals, He's Engaged
Still, Hasselhoff admits that playing second fiddle to a four-wheeler has its problems. "Once at L.A. airport," he recalls, "this woman ran up to me and hugged me and turned to her husband and said, 'I've been watching him on TV. Isn't he gorgeous?' The husband snarled, 'You're nothing without that car.' I got angry and asked him, 'Why don't you ask for the car's autograph?' I'm too sensitive—it's something I have got to get over."
David certainly never encountered such problems during his six years as heartthrob "Snapper" Foster on the CBS soap The Young and the Restless. When he resigned from the serial last year, he had "only" $30,000 in the bank and "didn't know where I was going, but I knew I had to leave." His worries were quickly alleviated by Brandon Tartikoff, president of NBC Entertainment, who invited him to try out for Knight Rider (Hasselhoff's first prime-time series, 1980's Semi-Tough, expired after four episodes).
The screen test was a near disaster. Hasselhoff climbed into the Pontiac Trans Am and "couldn't remember one line. I asked for five minutes to get it together, went backstage and shouted at myself, 'You are the Knight Rider!' I walked back in and did the scene dead on." He won the part. "I was so excited I literally screamed for joy," recalls Hasselhoff, who now rakes in more than $15,000 a week—compared to $5,400 during his soap opera days.
The new series also has paid off for Hasselhoff's live-in girlfriend, Catherine Hickland, 27, a 5'5" green-eyed blonde who played the young, romantic Courtney Marshall in the 1980-82 soap Texas. Hickland recently created the story line and starred in a Knight Rider episode called "White Bird," and she and David became engaged the day the episode wrapped. (She now sports a carat-and-a-half diamond engagement ring she calls "Gibraltar in a setting.")
Hasselhoff and Hickland met at the 1981 Daytime Emmy Awards in New York. "He begged me for a date and I said 'No,' " she laughs. "I'm generally not attracted to 6'4" men who look like Ken dolls," sasses Catherine. "They're too much trouble with their egos. He went back to L.A. and called me every other night screaming, 'I'm in love with you,' but I kept saying, 'No, no, no.' Then in September I came to L.A. on a business trip. We went out together and we've been together ever since." A member of a nondenominational church called the Hiding Place (Stevie Nicks of Fleetwood Mac recently married a church member), Catherine wears a small gold "Try God" pendant and carries her Bible everywhere. "I don't think David's too crazy about it," she says, though Hasselhoff, a lapsed Catholic, confides, "It doesn't faze me."
Born in Baltimore, son of a Brinks executive and a "housewife and stage mother," Hasselhoff started acting in school at age 7, had leading roles in high school productions, and worked dinner theaters in Chicago before arriving in L.A. in 1971. He broke into soap operas after a top agent, the late Joyce Selznick, discovered him in 1975 when he was a waiter. His new wealth has enabled Hasselhoff and Catherine to bid on a $450,000 four-bedroom home on Mulholland Drive, complete with requisite swimming pool and panoramic view of L.A. Until negotiations are complete, they'll share David's messy one-bedroom home in the Hollywood Hills with two cats and three parrots.
Off the Knight Rider set, Hasselhoff spends his time making personal appearances for NBC and Pontiac and visiting terminally ill and handicapped children. ("Because I am 'Michael Knight,' I can make kids smile," he explains.) He is also one of the founders and owners of the Ideas That Sell Toy Company, which so far has marketed 500,000 "rag balls" at $3.95 each. ("It acts like a hardball but doesn't hurt if it hits you.") Hasselhoff admits to being somewhat hurt by jokes about his show and his acting ability (the Washington Post called him a "zero" in one review), but he knows it's all part of the trade. "I think what Catherine likes best about me is my sense of humor," he says. "If you lose that in this town, you might as well not go on."
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Mozilla Firefox 30 Binaries Now Available
Published on 10 June 2014 12:01 AM EDT
Written by
Michael Larabel
20 Comments
The Firefox 30 release announcement is imminent with the source and binaries for the upcoming browser update now being available.
For those interested, Mozilla Firefox 30.0 can be obtained from the
Mozilla FTP server
while we're still waiting for the official release announcement, which is likely coming in the day ahead.
For Linux users, Mozilla Firefox 30 is important in that
it finally supports GStreamer 1.0
. Firefox 30 also boasts improvements to the Australis user-interface. Other changes for Firefox 30 include HDMI improvements, new JavaScript ES6 improvements, a variety of new APIs supported for developers, and a variety of other additions and alterations. Those in a rush to find out Firefox 30 changes can find a tentative list via the
30.0 beta release notes
20 Comments
News Archives
Recent Mozilla News
Mozilla Developer Experimenting With Firefox UI In HTML
Firefox 34 Brings Its Improved Search Bar, Firefox Hello
Yahoo To Become Default Search Provider For Firefox
VP8 & H.264 Become Mandatory For Browsers With WebRTC Support
Firefox OS 2.0 Developer Preview Gets WebNFC, H.264 Hardware Encode/Decode
Mozilla Launches Firefox Developer Edition
Mozilla's Servo Engine Is Crazy Fast Compared To Gecko
Mozilla Is Launching A New Web Browser Targeting Developers
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Burton Mix Master Gloves (video)
If you can afford to ski the slopes this winter than you'll probably have enough cash to throw down for these iPhone compatible gloves from Burton that cost $160.
The name, Mix Master Glove (and Mitt) – we hope it has nothing do with that MTV Spring Break DJ – as the moniker suggests, allows you to control your iPhone's tunes simply by tapping on the gloves Fibretronic controls. Keep in mind you'll probably want a pair of wireless headphones to complete your wireless nirvana, but that's entirely up to you.
Burton also thought about a use case off the slopes. The remote is removable and can be used in your car or any where you would like to control your tunes from afar. It uses RF so line of sight isn't needed and will work within 100-feet of the receiver.
The Mix Master Gloves have a waterproof DRYRIDE Insane Membrane, Gnar Guard genuine leather exterior, and quick-drying microfiber lining. So yes, they're actual gloves that will keep you warm and dry.
Christen Costa
Grew up back East, got sick of the cold and headed West. Since I was small I have been pushing buttons - both electronic and human. With an insatiable need for tech I thought "why not start a blog focusing on technology, and use my dislikes and likes to post on gadgets."
Related Posts
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The Floating Mars Bluetooth Speaker Levitates Your Music
Just-released HP 7 Plus Tablet already $15 off & $40 GPS with lifetime maps/traffic
6 Things You Need To Know About the Latest Huawei Ascend P7 (list)
New iPad Images Leaked, Shows a Space Gray Colorway


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Some holiday tournaments are done, with more still to come, leading to a bit of fluctuation in the rankings.
Defending national champ Blackman makes surge after defeating local foe Oakland.
Long Beach Poly moves from unranked to third and Bishop McNamara, Montini enter as well.
Team: Football ( Philly.com - 11/12/2014)
Team: Football ( Ted Silary - 11/2/2014)
Team: Football ( Ted Silary - 9/21/2014)


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Holdays.net Home
Notice the rug can be flipped over to show the same pattern with a different look. This reversible rug is perfect for use indoors or out since it is made from recycled polypropylene. Each rug comes with a jute bag for storage or transport to the Beach or Park ... anywhere you want to relax and enjoy your time with family and friends. and did I mention you are recycling?choose a 3' x 5' for $38 - 4' x 6' for $48 - 5' x 8' for $89 - 6' x 9' for $118Actual Size 3'x5'(35"x58") - placemats12"x19" - 2.5'x8'(29"x94") - 4'x6'(47"x70") - 5'x8'(59"x94") - 6'x9'(71"x106")- Washable - Just shake or hose off for easy cleaning - Suitable for indoor and outdoor uses - Portable for use in picnics and camping trips - Reversible - Change the look of your décorWe carry a very large line of Cast Iron urns Trellises, Arbors, Garden Decor and Wrought Iron Fence. Go to our store by clicking this red door
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Outdoor Artificial Turf Wine Synthetic Grass Carpet


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User review spotlight: Ultima IV: Quest of the Avatar (DOS)
Title screen
The opening story
The opening story continued
Starting a new game
Watch out for giant critters
More enemies coming your way
Celebrating 15 years of game documentation. Information, credits, reviews, screenshots and more covering 145 video game platforms from 1971 to date!
MobyGames™ Copyright © 1999-2014
Blue Flame Labs. All rights reserved.
Terms of Use.
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Clark Ellis brings us a rare interview with British researcher Dr. Jonathan Kerr who is now living in Colombia.
Discuss the article on the Forums.
Does De Meirleir have concerns about the xmrv serology test?
Discussion in 'XMRV Testing, Treatment and Transmission' started by Berthe, Sep 30, 2010.
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Recent Metro reviews
"We COMPLETELY enjoyed our stay in this home. Very clean, and beautiful views! Will be staying here again next year!"Guest: Jay G. Date of Stay: September 2014 Review Submitted: October 2, 2014View listing
"Stayed at this delightful cottage in June. Convenient and easy to get to from the Twin Cities. Once there, practically lived on the screen porch - feels like you are outside right by the river (without the nuisance of mosquitoes). As noted, it is an older cottage but it has been well maintained and is clean. Loved the decor. The pictures on their site capture it well. It's a great place for a retreat, but parks, towns and activities near by if you want to venture out. The owners are friendly and attentive - ready to help with whatever you need, but they are also not intrusive. I've recommended this place to others and hope to return."Guest: Karla and Ken Date of Stay: June 2014 Review Submitted: August 8, 2014View listing
"First trip to Minneapolis. We were in the city for back to back national volleyball tournaments with our teenage daughters. I will say that everyone else who stayed at the hotels was GREEN with envy. Great location, fabulous amenities, recommendations for shopping/dining were so helpful, neighbors were friendly!! Kelly was a gem to work with. I would HIGHLY recommend. I would return in a second!"Guest: Tracy H Date of Stay: June 2014 Review Submitted: November 25, 2014View listing
"House exactly as described, in a quiet neighbourhood. My family enjoyed our time there, owner answered any queries we had promptly. We had travelled from England and it was great to be able to relax in this lovely home. We shopped at Lunds grocery store a short walk away but well worth it. A pleasure to rent from this owner, I would recommend this house to anyone wanting to explore the Twin Cities."Guest: AMANDA RYDER Date of Stay: August 2014 Review Submitted: September 2, 2014View listing
Featured Destinations: The Villages, Rosemary Beach, Destin, Amelia Island, Myrtle Beach, Outer Banks


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Computer Class
Computer Basics. April 22. 2:00 p.m.Submitted by oplin on Fri, 02/28/2014 - 3:55pm
This class will help students become familiar with their computer and is foundational for other computer classes such as Word 101 and Word 102.
Readers' Advisory on the WebSubmitted by oplin on Fri, 02/28/2014 - 3:38pm
This class will review a variety of readers' advisory websites.
Read for L.I.F.E. Open Computer LabSubmitted by oplin on Wed, 02/26/2014 - 10:22am
Are you a R.E.A.D. for L.I.F.E student that would like some extra time on the computer? Come to the open computer lab and experience a relaxed environment where you can work on a variety of computer skills. A library staff member will be available to help you. Helpful handouts will be provided to get you started. Topics include typing skills, resumes, the new GED, e-mail and more. Tutors welcome. Please register in the READ for L.I.F.E. office.
Non Library EventSubmitted by oplin on Wed, 02/26/2014 - 10:01am
Word 101Submitted by oplin on Wed, 02/19/2014 - 4:00pm
Learn the basics of Word 2010. Some of the information covered includes: formatting text, page layout, indents and tabs, line and paragraph spacing.


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Dextrose Monohydrate Industry - Global & China Development Ana...2014 Deep Research Report on Global Dextrose Monohydrate Industry" is a professional and in-depth research report on the Global and China Dextrose Monohydrate market. The report provides basic Dextrose Monohydrate information, including the Dextrose ... Minyanville, 1 month ago
Dextrose Monohydrate Industry Global & China Development Analysis in a New Research Report Now at DeepResearchReports.com - Tutorial Finder, 1 month ago
Dextrose Monohydrate Industry Global & China Development Analysis in a New Research Report Now at DeepResearchReports.com - Virtual Strategy Magazine, 1 month ago
More from: Stock Nod, Town Hall...and 23 other sources
Nihon Kohden Dominating High-Tech Asia-Pacific Patient Monitoring Market, Chased by Philips Healthcare, GE Healthcare, and Fukuda Denshi
According to a report by iData Research (http://www.idataresearch.com), the multi-parameter vital sign monitoring market segment in the Asia-Pacific region is both stable and exceptionally valuable; over the next few years, this segment will ...4 Traders, 2 months ago
Single-Lead ECG Machines Market: Global Industry Analysis and Forecast to 2020
Persistence Market Research is released new forthcoming report on title " ". New York, NY -- (ReleaseWire) -- 11/20/2014 -- Cardiovascular diseases are the leading cause of death across the globe. These are diagnosed with the help of ECG. An ...Digital Journal, 4 weeks ago
Global Glass Packaging Market 2014-2018
FEATURED COMPANIES Amcor Bormioli Rocco Gerresheimer Nihon Yamamura Glass Saint-Gobain Vidrala MORE About Glass Packaging Glass packaging is one of the most popular ...Research and Markets, 2 months ago ReportsnReports.com: Global Glass Packaging Market to Grow at 3.18% CAGR by 2018 BusinessWeek, 2 months ago Global Glass Packaging Market to Grow at 3.18% CAGR by 2018 Individual.com, 2 months ago
Cardiac Monitoring And Diagnostic Devices - Global Trends, Estimates and Forecasts, 2012-2018
DUBLIN , Dec. 19, 2014 /PRNewswire/ -- Research and Markets (http://www.researchandmarkets.com/research/nv5b3j/cardiac) has announced the addition of the " " report to their offering. http://photos.prnewswire.com/prnh/20130307/600769 The ...ADVFN India, 12 hours ago Electrophysiology (EP) Ablation Catheters - Global Trends, Estimates and Forecasts, 2012-2018 ADVFN India, 12 hours ago Prosthetic Heart Valves - Emerging Markets (Brazil, Russia, India, China, South Africa And South Korea), 2012-2018 TheStreet.com, 12 hours ago Cardiac Rhythm Management (CRM) Devices - Global Trends, Estimates and Forecasts, 2012-2018 Reuters, 12 hours ago
Half Yearly Report
Regulatory Story Atlantis Japan Growth Fund Ld - AJG Released 16:52 17-Dec-2014 RNS Number : 0998A Atlantis Japan Growth Fund Ld 17 December 2014 ATLANTIS JAPAN GROWTH FUND LIMITED ("AJGF" or the "Company") (A closed-ended investment company ...London Stock Exchange, 2 days ago
Nippon Chemiphar : Establishment of a Joint Venture in Vietnam Through our Subsidiary NPI (pdf, 120KB)
Establishment of a JV in Vietnam through our subsidiary E STABLISHMENT OF A J OINT V ENTURE IN V IETNAM T HROUGH OUR S UBSIDIARY NPI Nippon Chemiphar Co., Ltd. (TSE: 4539) December 4, 2014 Nippon Chemiphar Co., Ltd. (hereinafter "Chemiphar") ...4 Traders, 1 week ago Establishment of a Joint Venture in Vietnam Through our Subsidiary NPI (pdf, 120KB) Noodls, 1 week ago
The End of the Postwar? The Abe Government, Okinawa, and Yonaguni Island 戦後の終焉? 安倍政権、沖縄、そして与那国
Gavan McCormack 1 Framing the Problem(s) *16 November 2014: Okinawa prefecture elects as new Governor Onaga Takeshi, who campaigned on the core policy of stopping construction of a base for the US Marine Corps in Northern Okinawa *17 ...Japan Focus, 1 week ago
Deals - 10 December 2014
Allen & Gledhill has advised the Housing Development Board in respect of the issue of S$1.1 billion (US$834.9m) fixed rate notes, S$500 million (US$379.5m) due 2019 and S$600 million (US$455.36m) due 2026, under its S$32 billion (US$24.3m) ...In House Community, 1 week ago
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By a News Reporter-Staff News Editor at Biotech Week -- According to news reporting originating from Washington, D.C. , by NewsRx journalists, a patent application by the inventors Homma, Masayuki ( Narita -shi, JP); Kogure , Takahisa ( Narita -shi, ...4 Traders, 3 weeks ago
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Latest Krishna Prasad Sitaula Stories
2006-06-15 08:10:10
By Simon Denyer and Gopal Sharma POKHARA, Nepal (Reuters) - Nepal's government and Maoists held fresh peace talks on Thursday, and both sides said rebel chief Prachanda would meet the country's prime minister and party leaders soon.
2006-05-18 01:08:21
By Gopal Sharma KATHMANDU (Reuters) - Nepal's parliament was set to pass a special resolution on Thursday that aims to curtail the king's powers and wrest control of the army from the monarch.
Word of the Day
- In dressmaking, straps running from the belt in front over the shoulders to the belt in the back, with more or less elaboration of trimming and outline. They usually broaden at the shoulder and narrow toward the waist.
The word 'bretelles' comes from a French word meaning 'braces'.


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Find 1 Apartments Near the Southeast Redmond Neighborhood in Redmond, WA
More Info
The Southeast Redmond neighborhood is a part of Redmond, WA. ForRent.com, an apartment finder service, makes your Southeast Redmond rental search easy. Let us guide your search for rentals from the apartments for rent listings provided. To narrow down your search, select from the Southeast Redmond beds, baths, price, type and amenity links below.
Showing 1 - 1 of 1 apartments found
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Featured Apartments in Redmond, WA
Elan Redmond Town Center
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- Redmond, WA
- Work 1-866-382-9503
- 47.673152536154 -122.1222987771
Redmond, WA 98052
Avalon Redmond Place
- Flexible and Customized Leasing Terms
- On The Sammamish River Trail
- Full size Washer/Dryer
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- Close To Microsoft & Highway 520
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Avalon Redmond Place apartments are located in desirable Redmond WA, on the edge of the Burke-Gilman Trail. We offer thoughtfully designed one bedroom, two bedroom, and three bedroom apartments, and each of our Washington apartment rentals features a gourmet kitchen, ample storage, and a lot of other highly desired features.
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I had to make last minute arrangements for my school group. We booked nine rooms within 48 hours of our scheduled arrival. The reservation was handled quickly and professionally. The hotel staff checked us in and out efficiently. The property was impeccable! The rooms were spacious, nicely furnished, sparkling clean. The breakfast room was well tended and spacious as well. The location was convenient with many good restaurants in the area. We travel to a competition in Warner Robins every October. We will definitely stay here again!
- Reservation Options:
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The ULTIMATE Princess Bride Test
Their result for The ULTIMATE Princess Bride Test ...
Congratulations! You scored ###!
Their Analysis (Vertical line = Average)
They scored 95% on Westley-ness, higher than 93% of your peers.
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No one really likes you, and besides, Westley tricked you in the iocane switch cup game. You better watch the movie a little more and take this test again, and try to be not so inconceivably stupid at... Read more
Big, somewhat kind, but not very smart. At least you know better than Vizzini! Put your brains in front of your brawn, and try again. Read more
Hello. My name is Inigo Montoya. And you did so-so on this test. Not the greatest, but not the worst either. By the time you find the man with six fingers on his hand, I'm sure you'll be at the top of... Read more
Oh, to be the title character, but still not at the top. It's tragic, no? Keep at it, and one day, your happy ending will come. Read more
Inconceivable! You've done it! You've bested my test! I drop my hat to you, good sir (or madam) and congratulate you on a job well done. See, you paid attention! Read more
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text:
41 years of experience
41 years of experience
1919 N Amidon Ave
Wichita, KS 67203 Phone number & directions
Wichita, KS 67203 Phone number & directions
License & Identifications
A medical license is required for a doctor to practice medicine in a particular state. Requirements vary by state but most require, at a minimum, post-graduate training in the doctor's specific specialty. An NPI number is a national identifier unique to an individual health care provider and is managed by the Center for Medicare & Medicaid Services (CMS).
Learn more about Dr. Poly Tan:
View the full profile to get information on:
- Qualifications
- What's important to you
View full profile
Patient Reviews
Have you visited Dr. Tan? Share your experience.
Write a Review
Write a Review
Specialties & Research
Dr. Poly Tan, MD is board certified in Psychiatry.
Education & Awards
Dr. Tan graduated from University of Oklahoma , Oklahoma City.
Dr. Tan has 1 hospital affiliations:
- Parkside PSYCH
Home > Find a Psychiatrist > KS > Wichita Psychiatrists > Dr. Poly Tan, MD
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- Additional Information
- Dr. Poly Tan MD is a male Psychiatrist, has 41 years of experience and practices in Psychiatry.
- Where does Dr. Poly Tan practice?
- Dr. Poly Tan has 1 office location.
Dr. Poly Tan practices Psychiatry near Wichita, KS.
See Wichita Psychiatrists.


text:
Mortgages from the F.H.A. and Department of Veterans Affairs have a little-known feature: assumability.
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Debe Maxwell www.iCharlotteRealEstate.com's curator insight, July 3, 11:13 PM
Still an issue here in Charlotte!


text:
Many of us at Windows Central have been using Tweetium for Windows Phone and Windows for months now, but the Windows Phone Twitter client was technically in beta.
No more as starting today, the Windows Phone app is no longer beta and both have jumped in version numbers to 3.0. What's more, a brand new color accent scheme is now in place, making these Modern apps even more appealing.
Brandon Paddock, the developer behind the Tweetium apps, is never shy about giving detailed changelogs. Version 3.0 is no exception as the app has had some significant improvements over the last 24-hours.


text:
Credits & Info
- Uploaded
- Feb 16, 2001 | 8:40 PM EST
If you liked this, check these out!
Plenty more like this here!
All Your Base Learn the history of the AYB phenomenon, then watch the original movie and many spin-offs!
Author Comments
Rated 5 / 5 stars
Even over a decade later it's as good as it was back then.
On a side note- it's strange watching an internet meme video that is older than my little sister; a twelve year old.
Rated 5 / 5 stars
loved this, cant get it oput of my head
Rated 5 / 5 stars
Hm. I thought there would be more views than 2 million. This video....eh.... more and more random energys these days. tune into the pure self my bretheren.
Rated 5 / 5 stars
Wow, we were so easily entertained back then weren't we?
Rated 5 / 5 stars
This movie gave me a good laugh also l fucking love the grammar in japanese games :D