CO oxidation over Au/TiO2 prepared from metal-organic gold complexes

A series of Au/TiO₂ catalysts has been prepared from precursors of various metal-organic gold complexes (Au _n , n = 2–4) and their catalytic activity for CO oxidation studied. The Au/TiO₂ catalyst synthesized from a tetranuclear gold complex shows the best performance for CO oxidation with transmission electron microscopy of this catalyst indicating an average gold particle size of 3.1 nm.     

Supported gold catalysis in the hydrogenation of canola oil

The catalytic activity of gold supported on silica orγ-alumina has been studied in the hydrogenation of canola oil. In the hydrogenation of butadiene and pentene using these catalysts, high stability, low yield oftrans-isomers and high monoene selectivity have been reported in the literature. Catalysts containing 1% and 5% Au w/w on porous silica andγ-alumina were active in hydrogenating canola oil in the range of 150 to 250 C and 3550 to 5620 kPa. The activity level of these catalysts was about 30 times lower than that shown by the standard AOCS Ni catalyst based on the concentration of metal (g Au/L oil). Up to 91% monoene content was obtained using these catalysts in comparison with a maximum of 73% for the AOCS standard Ni catalysts. Gold catalysts can be recovered easily by filtration and reused several times without a decrease in activity. The hydrogenated oil was nearly colorless. No gold was detectable in the oil. Contrary to claims in the patent literature, the gold catalyst produces higher concentrations oftrans-isomers than does nickel. However, using gold catalysts the complete reduction of linolenic acid in canola oil can be achieved at a lowertrans-isomer content in the products than that obtained by using the AOCS standard nickel catalyst.     

Impedance studies of copper electro-reduction on a disc-shaped ultramicroelectrode in industrial electrolytes

The electrodeposition of copper from industrial sulphate electrolytes has been studied using electrochemical impedance spectroscopy on the gold disc ultramicroelectrode. The influence of dc potential E _dc , temperature, cupric ions and animal glue concentration on electrochemical impedances has been investigated. The mechanism of the copper electro-reduction process in industrial electrolytes has been proposed and experimental impedance data have been analyzed by proper equivalent circuits. According to our knowledge the faradaic and non-faradaic impedance parameters of the process on ultramicroelectrode’s have been estimated for the first time in complex matrix copper industrial electrolytes. The role of animal glue in copper industrial electrolytes has been discussed in the present paper.     

Synthesis, characterization, and antibacterial activity of metal nanoparticles embedded into amphiphilic comb-type graft copolymers

The synthesis, spectroscopic characterization, and antimicrobial efficiency of gold and silver nanoparticles embedded in novel amphiphilic comb-type graft copolymers having good film-forming properties have been described. Amphiphilic comb-type graft copolymers were synthesized by the reaction of chlorinated polypropylene (PP) (M _w = 140,000 Da) with polyethylene glycol (PEG) (M _n  = 2,000 Da) at different molar ratios. Metal nanoparticles embedded graft copolymers were prepared by reducing solutions of the salts of silver or gold and the copolymer in tetrahydrofuran. The optical properties of the metal nanoparticle embedded copolymers were determined by using UV–visible spectroscopy. Surface plasmon resonance (SPR) of the gold and silver nanoparticle embedded copolymers in toluene was observed at a maximum wavelength (λ_max) of 428 and 551 nm in the UV–VIS absorption spectra, respectively. The average particle diameters of the gold and silver nanoparticles were found to be 50 nm from the high resolution scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Amphiphilic polymer films containing silver and gold nanoparticles were found to be highly antimicrobial by virtue of their antiseptic properties to Escherichia coli and Staphylococcus aureus.     

Recent advances in the biochemistry and clinical relevance of the isoprostane pathway

Isoprostanes (IsoPs), lipid peroxidation products formed via the free radical-mediated oxidation of arachidonic acid, have become the “gold standard” biomarker of oxidative stress in vivo over the past 15 yr. Significant advances have been made in understanding this important pathway of lipid peroxidation. Recent studies from our laboratory are discussed that have provided insights into the mechanism of formation and regioisomeric distribution of these compounds and that have identified novel products of the IsoP pathway such as cyclized dioxolane IsoPs, IsoP-derived racemic prostaglandins, and reactive cyclopentenone IsoP, the latter of which possess potent biological actions. Furthermore, new independent studies have demonstrated that IsoPs are the most reliable available marker of lipid peroxidation in vivo, and recent work examining IsoP formation has provided valuable infromation about the pathogenesis of numerous human diseases. Thus, the complexity of the IsoP pathway has expanded, providing novel insights into mechanisms of lipid peroxidation in vivo and allowing investigators to explore the role of oxidative stress in human disease.     

Electrochemical sensor for bisphenol A detection based on molecularly imprinted polymers and gold nanoparticles

A novel bisphenol A (BPA) sensor based on amperometric detection has been developed by using molecularly imprinted polymers (MIPs) and gold nanoparticles. The sensitive layer was prepared by electropolymerization of 2-aminothiophenol on a gold nanoparticles-modified glassy carbon electrode in the presence of BPA as a template. Cyclic voltammetry was used to monitor the process of electropolymerization. The properties of the layer were studied in the presence of Fe(CN)₆ ³⁻/Fe(CN)₆ ⁴⁻ redox couples. The template and the non-binding molecules were removed by washing with H₂SO₄ (0.65 mol L⁻¹) solution. The linear response range of the sensor was between 8.0 × 10⁻⁶–6.0 × 10⁻² mol L⁻¹, with a detection limit of 1.38 × 10⁻⁷ mol L⁻¹ (S/N = 3). The proposed MIPs sensor exhibited good selectivity for BPA. The stability and repeatability of the MIPs senor were found to be satisfactory. The results from real sample analysis confirmed the applicability of the MIPs sensor to quantitative analysis.     

Electrochemical detection of the neomycin phosphotransferase gene (NPT-II) in transgenic plants with a novel DNA biosensor

A novel DNA electrochemical biosensor is described for the detection of neomycin phosphotransferase gene (NPT-II), a selection marker for transgenic plants. A thiol-modified capture probe immobilized onto the surface of a gold electrode and a biotinylated signaling probe were designed to be complementary to target regions of NPT-II flanked by PCR primers to eliminate false-positive signals from non-specific PCR products. The electrochemical assay of hybrids on the electrode surface was evaluated by means of both cyclic voltammetry (CV) and square wave voltammetry (SWV) after the coupling of biotinylated catalase with streptavidin-modified hybrids based on dendritic signal magnification and subsequent formation of polymerized aniline (PAn). It has been revealed that the sensor showed a linear increase within the target concentration (1.0–100 × 10⁻⁶ mmol L⁻¹). The limit of detection was about 0.2 × 10⁻⁶ mmol L⁻¹ and the specificity was enhanced significantly.     

Electrochemical simultaneous determination of nitrophenol isomers at nano-gold modified glassy carbon electrode

A novel method for simultaneous determination of nitrophenol isomers at nano-gold modified glassy carbon electrode has been developed. The gold nanoparticles were directly electrodeposited onto the glassy carbon electrode via a constant potential −0.2 V (vs. SCE) for 60 s from 0.1 mol L⁻¹ KNO₃ containing 0.4 g L⁻¹ HAuCl₄. The resulting electrode (nano-Au/GCE) was characterized with scanning electron microscopy (SEM). The electrochemistry response of nitrophenol isomers at the nano-Au/GCE was studied. The result indicated that o-, m-, and p- nitrophenol are separated entirely at nano-Au/GCE, and a semi-derivative voltammetric technology was adopted to enhance the determination sensitivity. This modified electrode could be applied to direct simultaneous voltammetric determination of nitrophenol isomers in water samples without preseparation with higher sensitivity.     

Bulk Gold-Catalyzed Oxidations of Amines and Benzyl Alcohol Using Amine N-Oxides as Oxidants

Abstract  

Bulk gold powder (~50 μm) catalyzes the oxidative dehydrogenation of amines to give imines using amine N-oxides (R₃N-O) as the oxidant. The reaction of dibenzylamine (PhCH₂–NH–CH₂Ph) with N-methylmorpholine N-oxide (NMMO) in the presence of gold powder at 60 °C produced N-benzylidenebenzylamine (PhCH=N–CH₂Ph) in 96% yield within 24 h. Benzyl alcohol was oxidized by NMMO to benzaldehyde in >60% yield in the presence of gold powder. Although O₂ was previously shown to oxidize amines in the presence of bulk gold, it is surprising that gold is also capable of catalyzing the oxidation of amines using amine oxides, which are chemically so different from O₂.     

Fabrication of Anti-human Cardiac Troponin I Immunogold Nanorods for Sensing Acute Myocardial Damage

A facile, rapid, solution-phase method of detecting human cardiac troponin I for sensing myocardial damage has been described using gold nanorods-based biosensors. The sensing is demonstrated by the distinct change of the longitudinal surface plasmon resonance wavelength of the gold nanorods to specific antibody–antigen binding events. For a higher sensitivity, the aspect ratio of gold nanorods is increased up to ca 5.5 by simply adding small amount of HCl in seed-mediated growth solution. Experimental results show that the detecting limit of the present method is 10 ng/mL. Contrast tests reveal that these gold nanorods-based plasmonic biosensors hold much higher sensitivity than that of conventionally spherical gold nanoparticles.     

In situ–Directed Growth of Organic Nanofibers and Nanoflakes: Electrical and Morphological Properties

Organic nanostructures made from organic molecules such as para-hexaphenylene (p-6P) could form nanoscale components in future electronic and optoelectronic devices. However, the integration of such fragile nanostructures with the necessary interface circuitry such as metal electrodes for electrical connection continues to be a significant hindrance toward their large-scale implementation. Here, we demonstrate in situ–directed growth of such organic nanostructures between pre-fabricated contacts, which are source–drain gold electrodes on a transistor platform (bottom-gate) on silicon dioxide patterned by a combination of optical lithography and electron beam lithography. The dimensions of the gold electrodes strongly influence the morphology of the resulting structures leading to notably different electrical properties. The ability to control such nanofiber or nanoflake growth opens the possibility for large-scale optoelectronic device fabrication.     

Biomimetic Synthesis of Gelatin Polypeptide-Assisted Noble-Metal Nanoparticles and Their Interaction Study

Herein, the generation of gold, silver, and silver–gold (Ag–Au) bimetallic nanoparticles was carried out in collagen (gelatin) solution. It first showed that the major ingredient in gelatin polypeptide, glutamic acid, acted as reducing agent to biomimetically synthesize noble metal nanoparticles at 80°C. The size of nanoparticles can be controlled not only by the mass ratio of gelatin to gold ion but also by pH of gelatin solution. Interaction between noble-metal nanoparticles and polypeptide has been investigated by TEM, UV–visible, fluorescence spectroscopy, and HNMR. This study testified that the degradation of gelatin protein could not alter the morphology of nanoparticles, but it made nanoparticles aggregated clusters array (opposing three-dimensional α-helix folding structure) into isolated nanoparticles stabilized by gelatin residues. This is a promising merit of gelatin to apply in the synthesis of nanoparticles. Therefore, gelatin protein is an excellent template for biomimetic synthesis of noble metal/bimetallic nanoparticle growth to form nanometer-sized device.     

On the Enhanced Antibacterial Activity of Antibiotics Mixed with Gold Nanoparticles

The bacterial action of gentamicin and that of a mixture of gentamicin and 15-nm colloidal-gold particles on Escherichia coli K12 was examined by the agar-well-diffusion method, enumeration of colony-forming units, and turbidimetry. Addition of gentamicin to colloidal gold changed the gold color and extinction spectrum. Within the experimental errors, there were no significant differences in antibacterial activity between pure gentamicin and its mixture with gold nanoparticles (NPs). Atomic absorption spectroscopy showed that upon application of the gentamicin-particle mixture, there were no gold NPs in the zone of bacterial-growth suppression in agar. Yet, free NPs diffused into the agar. These facts are in conflict with the earlier findings indicating an enhancement of the bacterial activity of similar gentamicin–gold nanoparticle mixtures. The possible causes for these discrepancies are discussed, and the suggestion is made that a necessary condition for enhancement of antibacterial activity is the preparation of stable conjugates of NPs coated with the antibiotic molecules.     

Synthesis and Characterization of Cellulose α-Lipoates: A Novel Material for Adsorption onto Gold

Summary Novel α-lipoic acid esters of cellulose (cellulose α-lipoates) were synthesized homogeneously in N,N-dimethylacetamide (DMAc)/LiCl using different methods for the in situ activation of the carboxylic acid. Thus, cellulose α-lipoates with degrees of substitution (DS) in the range 0.11 to 1.45 were accessible with N,N’-carbonyldiimidazole and p-toluenesulphonyl chloride as in situ activating agents for the α-lipoic acid. The reactions proceeded totally homogeneous with high yields giving cellulose α-lipoates soluble in DMSO. The α-lipoate moiety containing a S-S function stays intact during the reaction as revealed by FTIR and ¹H NMR spectroscopy. The cellulose α-lipoates showed self-assembly onto gold surface yielding layers with a thickness of 2.9–4.9 nm, which can be confirmed by surface plasmon resonance. The perpropionylated cellulose α-lipoates form films with a comparably low thickness of 0.9 nm.     

CO Oxidation Over a Fine Porous Gold Catalyst Fabricated by Selective Leaching from an Ordered AuCu3 Intermetallic Compound

A fine porous gold catalyst has been fabricated by selective leaching of Cu from an ordered AuCu₃ intermetallic compound with 50%HNO₃ aqueous solution at 50 °C. This catalyst exhibited comparable areal rate (mol min⁻¹ m⁻²-cat) with the Au/TiO₂ catalyst for CO oxidation. The present study demonstrates that high catalytic activity of gold is originated neither from the presence of fine dispersed Au particles nor from Au-support perimeter interface.     

Chemical Synthesis of PEDOT–Au Nanocomposite

In this work, gold-incorporated polyethylenedioxythiophene nanocomposite material has been synthesized chemically, employing reverse emulsion polymerization method. Infrared and Raman spectroscopic studies revealed that the polymerization of ethylenedioxythiophene leads to the formation of polymer polyethylenedioxythiophene incorporating gold nanoparticles. Scanning electron microscope studies showed the formation of polymer nanorods of 50–100 nm diameter and the X-ray diffraction analysis clearly indicates the presence of gold nanoparticles of 50 nm in size.     

Solubilisation of gold by Cuhromobacterium violaceum

Chromobacterium violaceum, a cyanogenic bacterium, has been shown to solubilise up to 215 parts × 10^?6 gold from 1000 parts × 10^?6 of the pure metal after 40 days incubation in nutrient medium. Cyanide is produced during the growth and stationary phase of culture and the solubilised gold species has been shown to be the complex anion [Au(CN)₂]^?.     

Adsorption of palladium, platinum, and gold chloride complexes by carbon fibers with various structures

Data are given characterizing the effects of the porous structures in activated carbon fibers (ACF) and the amounts of oxidized carbon forms on the extent and rate of adsorption for various chloride complexes of the platinum metals and gold. The adsorption mechanisms on ACF are considered for these metal chloride complexes. The practical significance of the research is considered. Translated from Khimicheskie Volokna, No. 4, pp. 61–69, July–August, 2008.     

Templated Synthesis of Gold Nanorods (NRs): The Effects of Cosurfactants and Electrolytes on the Shape and Optical Properties

Seeded growth of gold nanorods (NRs) has been accomplished in a micellar medium containing mixed surfactants or a high salt concentration. Cetyl trimethylamoniumbromide (CTAB) forms micelles upon which the growth of rod shaped gold nanoparticles occurs. AgNO₃ is introduced into the growth solution to enhance the formation of NRs. The roles of non-ionic surfactants such as Tween and Triton, and of electrolytes such as sodium chloride and potassium chloride have been examined. As the concentration of these additives in the growth solution is increased, the aspect ratio of the NRs increases to a critical limit, after which it decreases again. Upon carefully controlling the content of Triton X-100 or Tween 20 in the growth solution, these non-ionic surfactants assisted in fine-tuning the shape of gold NRs (e.g. rectangular or “dogbone”). The growth pattern of the NRs fits into the model of a soft template formed by the mixture of CTAB and non-ionic surfactants.     

Influence of the presence of bubbles on the parameters of crystal nucleation in the 26Li<Subscript>2</Subscript>O · 74SiO<Subscript>2</Subscript> glass

The crystal nucleation in the glass of composition (mol %) 26Li₂O · 74SiO₂ has been investigated in the cases of homogeneous and heterogeneous nucleation. Parameters of homogeneous nucleation, such as the stationary nucleation rate I _st, the time of nonstationary nucleation τ, and the crystal growth rate U, have been determined. The temperature dependences of these parameters have been constructed. The surface energy σ at the nucleus-glass melt interface has been determined, and its temperature dependence has been obtained. The surface energy σ has been evaluated using the graphical method for solving the transcendental equation derived by transforming the relationships for the stationary crystal nucleation rate and the time of nonstationary crystal nucleation. The critical nucleus sizes r* and the free energy of formation of the critical nucleus Φ* have been determined. The heterogeneous nucleation on bubbles specially produced in the glass has been studied. It has been demonstrated that the presence of bubbles in the initial glass does not affect the crystal growth rate and substantially changes the nonstationary nucleation rate. The largest contribution to the change in the nucleation rate is made by “active” bubbles (filled by water vapor) formed in the glasses synthesized with the use of hydrated silicon dioxide.