Reducing HAuCl(4) by the C(60) dianion: C(60)-directed self-assembly of gold nanoparticles into novel fullerene bound gold nanoassemblies

The C(60) dianion is used to reduce tetrachloroauric acid (HAuCl(4)) for the first time; three-dimensional C(60) bound gold (Au-C(60)) nanoclusters are obtained from C(60)-directed self-assembly of gold nanoparticles due to the strong affinities of Au-C(60) and C(60)-C(60). The?process was monitored in situ by UV-vis-NIR spectroscopy. The resulting Au-C(60) nanoclusters were characterized using transmission electron microscopy (TEM), selected area electron diffraction (SAED), energy-dispersive spectroscopy (EDS), x-ray powder diffraction (XRD), x-ray photoelectron spectroscopy (XPS), and FT-IR and Raman spectroscopies. TEM demonstrates the formation of 3D nanonetwork aggregates, which are composed of discrete gold nanocores covered with a C(60) monolayer. The SAED and XRD patterns indicate that the gold nanocores inside the capped C(60) molecules belong to the face-centred cubic crystal structure, while the C(60) molecules are amorphous. The EDS and XPS measurements validate that the Au-C(60) nanoclusters contain only Au and C elements and Au(3+) is reduced to Au(0). FT-IR spectroscopy shows the chemiadsorption of C(60) to the gold nanocores, while Raman spectroscopy demonstrates the electron transfer from the gold nanocores to the chemiadsorbed C(60) molecules. Au-C(60) nanoclusters embedded in tetraoctyl-n-ammonium bromide (TOAB) on glassy carbon electrodes (GCEs) have been fabricated and have shown stable and well-defined electrochemical responses in aqueous solution.     

Thermally assisted semiconductor-like to insulator transition in gold-poly(methyl methacrylate) nanocomposites

Gold-polymethylmethacrylate (PMMA) nanocomposites were fabricated by mixing gold nanoparticles capped with oleylamine in polymethylmethacrylate. The samples were analysed using UV-vis absorption spectroscopy, transmission electron microscopy, small angle x-ray scattering, Fourier transform infrared spectrometry (FTIR) and x-ray photoelectron spectroscopy (XPS). Electrical resistivity of nanocomposite samples was measured by a four-probe technique in the 70-300?K range. The nanocomposites showed a transition with an onset at ～160-165?K. They exhibited a semiconductor-like conductivity at higher temperatures and nearly temperature independent conductivity at lower temperatures. The interfacial interaction of Au nanoparticles and PMMA polymer is investigated using FTIR and XPS. A ligand-exchange process occurs when capped gold nanoparticles are incorporated in PMMA polymer.     

Synthesis of tin oxide-coated gold nanostars and evaluation of their surface-enhanced Raman scattering activities

Tin oxide-coated gold nanostar hybrid nanostructures are prepared by first synthesizing gold nanostars (ca. 400 nm), then introducing Na₂SnO₃ precursor followed by its hydrolysis and formation of a tin oxide layer on nanoparticle surface. The synthesized hybrid structures have been characterized by combination of UV–Vis spectroscopy, transmission electron microscope (TEM), energy-dispersive X-ray studies, scanning electron microscope (SEM), X-Ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. The TEM and SEM analyses showed that gold nanostars have a coating with an approximate thickness of 15 nm. The tin (IV) oxide coating on the gold nanostars was identified by XRD and XPS analyses and confirmed by FTIR spectroscopy. Surface-enhanced Raman scattering (SERS) spectroscopy was performed on tin oxide-coated and uncoated gold nanostars with crystal violet as a probe molecule. The SERS studies revealed field enhancement properties of Au nanostars, thus their strong SERS activity remained after tin oxide coating.     

Structure of the Au-Rh bimetallic system formed on titanate nanowires and nanotubes

Au, Rh and Au-Rh nanoclusters were studied on one-dimensional titania nanostructures by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and infrared spectroscopy (FT-IR). On titanate nanowire and tube supports the gold 4f_7/2 XP emission appeared after reduction at 83.6 eV and 85.6 eV indicating two different sizes or chemical environments of gold nanoclusters. Small clusters also developed in rhodium containing samples besides the pure metallic state. Upon CO adsorption on the 1% Rh/titanate nanostructures the IR stretching frequencies characteristic of the twin (geminal) form were dominant, whereas bimetallic nanosystems featured a pronounced linear CO stretching vibration. At the same time the highest binding energy state disappeared almost completely indicating the enlargement of nanoclusters which was in agreement with SEM results. Very likely “core-shell” bimetallic clusters form, where gold covers the rhodium.     

Discrete charging effects in gold nanoclusters grown on self-assembled monolayers

Single electron charging effects were observed for gold nanoclusters grown on octanedithiol self-assembled monolayers by scanning tunneling microscopy and X-ray photoelectron spectroscopy (XPS). Strong interaction of gold with the terminal sulfur atoms of dithiol molecules on Au(111) suppresses effectively the penetration of deposited gold atoms through the dithiol layer and results in the formation of uniform metal nanoclusters. Decoupling of the clusters from Au(111) by the octanedithiol layer and the small self-capacitance of the nanoclusters realize the observation of the Coulomb blockade in scanning tunneling spectroscopy and the Au 4f core level shifts in XPS at room temperature. Both phenomena originate from a common physics, the Coulomb energy of charged particles.     

Discrete charging effects in gold nanoclusters grown on self-assembled monolayers

Single electron charging effects were observed for gold nanoclusters grown on octanedithiol self-assembled monolayers by scanning tunneling microscopy and X-ray photoelectron spectroscopy (XPS). Strong interaction of gold with the terminal sulfur atoms of dithiol molecules on Au(111) suppresses effectively the penetration of deposited gold atoms through the dithiol layer and results in the formation of uniform metal nanoclusters. Decoupling of the clusters from Au(111) by the octanedithiol layer and the small self-capacitance of the nanoclusters realize the observation of the Coulomb blockade in scanning tunneling spectroscopy and the Au 4f core level shifts in XPS at room temperature. Both phenomena originate from a common physics, the Coulomb energy of charged particles.     

Size exclusion chromatography for semipreparative scale separation of Au38(SR)24 and Au40(SR)24 and larger clusters

Size exclusion chromatography (SEC) on a semipreparative scale (10 mg and more) was used to size-select ultrasmall gold nanoclusters (<2 nm) from polydisperse mixtures. In particular, the ubiquitous byproducts of the etching process toward Au(38)(SR)(24) (SR, thiolate) clusters were separated and gained in high monodispersity (based on mass spectrometry). The isolated fractions were characterized by UV-vis spectroscopy, MALDI mass spectrometry, HPLC, and electron microscopy. Most notably, the separation of Au(38)(SR)(24) and Au(40)(SR)(24) clusters is demonstrated.     

Synthesis, characterization and application in electrocatalysis of polyaniline/Au composite nanotubes

Polyaniline (PANI) nanotubes were successfully synthesized using the hydrothermal method via an in situ polymerization. In the process, a fibrillar complex of FeCl(3) and methyl orange (MO), acting as the reactive self-degraded templates, directed the growth of PANI on its surface and promoted the assembly into nanotubular structures. By introducing PANI nanotubes into Au colloid, Au nanoparticles (NPs) could be decorated onto the PANI nanotube surface through the electrostatic effect. The morphology of the nanotubes and the number of decorated Au NPs could be controlled effectively by adjusting the experimental conditions. The resulting products were characterized by transmission electron microscopy (TEM), x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). In addition, the electrocatalytic activity of the composites towards the oxidation of NADH (nicotinamide adenine dinucleotide) was studied by immobilizing PANI/Au composites on the surface of a glassy carbon electrode (GCE).     

Method for measuring the melting temperature of gold nanoclusters on substrate surfaces

Results are reported from a study of low-energy electron scattering on Au nanoclusters on substrates of amorphous SiO₂ film and polycrystalline Ni at room temperature. When the height of the Au nanoclusters is reduced from 5 to 1 nm, their melting temperature is found to decrease from 1337 K (metallic gold) to 500 K. A simple method is proposed for measuring the thermodynamic characteristics (melting temperature and Debye temperature) of metallic nanoclusters on substrate surfaces.     

Anodic stripping voltammetry of arsenic(III) using gold nanoparticle-modified electrodes

A novel method for the detection of arsenic(III) in 1 M HCl at a gold nanoparticle-modified glassy carbon electrode has been developed. The gold nanoparticles were electrodeposited onto the glassy carbon electrode via a potential step from +1.055 to -0.045 V vs SCE for 15 s from 0.5 M H2SO4 containing 0.1 mM HAuCl4. The resulting electrode surfaces were characterized with both AFM and cyclic voltammetry. Anodic stripping voltammetry of arsenic(III) on the modified electrode was performed. After optimization, a LOD of 0.0096 ppb was obtained with LSV.     

Highly stable,protein capped gold nanoparticles as effective drug delivery vehicles for amino-glycosidic antibiotics

A method for the production of highly stable gold nanoparticles (Au NP) was optimized using sodium borohydride as reducing agent and bovine serum albumin as capping agent. The synthesized nanoparticles were characterized using UV–visible spectroscopy, transmission electron microscopy, X‐ray diffraction (XRD) and dynamic light scattering techniques. The formation of gold nanoparticles was confirmed from the appearance of pink colour and an absorption maximum at 532 nm. These protein capped nanoparticles exhibited excellent stability towards pH modification and electrolyte addition. The produced nanoparticles were found to be spherical in shape, nearly monodispersed and with an average particle size of 7.8 ± 1.7 nm. Crystalline nature of the nanoparticles in face centered cubic structure is confirmed from the selected‐area electron diffraction and XRD patterns. The nanoparticles were functionalized with various amino-glycosidic antibiotics for utilizing them as drug delivery vehicles. Using Fourier transform infrared spectroscopy, the possible functional groups of antibiotics bound to the nanoparticle surface have been examined. These drug loaded nanoparticle solutions were tested for their antibacterial activity against Gram-negative and Gram-positive bacterial strains, by well diffusion assay. The antibiotic conjugated Au NP exhibited enhanced antibacterial activity, compared to pure antibiotic at the same concentration. Being protein capped and highly stable, these gold nanoparticles can act as effective carriers for drugs and might have considerable applications in the field of infection prevention and therapeutics.     

Chemical functionalization of diatom silica microparticles for adsorption of gold (III) ions

Diatom silica microparticles from natural diatomaceous earth (DE) silica have been functionalized with 3-mercaptopropyltrimethoxysilane (MPTMS) and their application for adsorption of gold (III) ions from aqueous solutions is demonstrated. Fourier transform infrared spectroscopy (FTIR) and X-ray Photoelectron spectroscopy (XPS) analyses of the MPTMS modified diatom microparticles revealed that the silane layer with functional group (-SH) was successfully introduced to the diatom surface. The adsorption study of Au(III) ions using MPTMS-DE indicated that the process depends on initial gold (III) concentration and pH showing maximum adsorption capacity at pH = 3. The Au(III) adsorption kinetics results showed that the adsorption was very fast and followed a pseudo-second-order reaction model. The Langmuir model was used to provide a sound mechanistic basis for the theoretical of the adsorption equilibrium data. Gold recovery from MPTMS-DE structures was also investigated by using acidified thiourea solution and found to be high (> 95%). These results show that chemically modified DE microparticles can be used as a new, cost effective and environmentally benign adsorbent suitable for adsorption of gold metal ions from aqueous solutions.     

Gold/silicon nanocomposites: synthesis,characterization, and application in detection of dopamine

Silicon nanowires (SiNWs) with the length of several hundreds of micrometers and an average diameter of 15 nm were successfully synthesized via a thermal-evaporation oxide-assisted process. Then, a convenient method was applied to metallize the SiNWs just by dipping them into an aqueous deposition solution. During the metallization process, which is a redox reaction, gold nanoparticles (NPs) were prepared on SiNWs surface to confine the particle size and prevent agglomeration during the preparation and utilization of gold NPs. The synthesized SiNWs decorated with gold NPs were utilized to modify the glassy carbon electrode. Electrochemical measurements displayed that the modified electrode showed high sensitivity for dopamine (DA) detection.     

A cholesterol biosensor based on gold nanoparticles decorated functionalized graphene nanoplatelets

The fabrication of a cholesterol biosensor using gold nanoparticles decorated graphene nanoplatelets has been reported. Thermally exfoliated graphene nanoplatelets act as a suitable support for the deposition of Au nanoparticles. Cholesterol biosensor electrodes have been constructed with nafion solubilized functionalized graphene nanoplatelets (f-G) as well as Au nanoparticles decorated f-G, immobilized over glassy carbon electrode. f-G and Au/f-G thin film deposited glassy carbon electrodes were further functionalized with cholesterol oxidase by physical adsorption. Au nanoparticles dispersed over f-G demonstrate the ability to substantially raise the response current. The fabricated electrodes have been tested for their electrochemical performance at a potential of 0.2 V. The fabricated Au/f-G based cholesterol biosensor exhibits sensitivity of 314 nA/μM cm² for the detection of cholesterol with a linear response up to 135 μM. Furthermore, it has been observed that the biosensor exhibits a good anti-interference ability and favorable stability over a month's period.     

Synthesis of dendrimer-stabilized gold-polypyrrole core-shell nanoparticles

Core-shell composite nanoparticles consisting of a gold core and polypyrrole shell were prepared and stabilized with the poly(amidoamine) dendrimer. An in situ redox polymerization technique was used in which pyrrole reduced Au3+ to Au and then oxidized to polypyrrole. The presence of gold nanoparticles as a core was characterized by its surface plasmon absorption peak at 534 nm. Fourier transform infrared spectroscopy confirmed the presence of polypyrrole on the nanoparticle surfaces. The average diameter of the core-shell nanoparticle is 8.7 +/- 1.8 nm with a shell thickness of approximately 1.5-2.0 nm as estimated from the transmission electron microscopy image. Dissolution of the Au core using KCN enabled the formation of hollow polymer nanospheres.     

Peptide-assisted synthesis of gold nanoparticles and their self-assembly

A novel gold nanoparticle-tripeptide (GNP-tripeptide) conjugate was prepared by peptide in-situ redox technique at ambient temperatureusing a newly designed tripeptide. This new tripeptide was nso designed that it has a C-terminus tyrosine residue, which reduced Au+3 to Au, and the terminally located free amino group was bound to the gold nanoparticle (GNP) surface resulting in highly stable Au colloids. The average diameter of the tripeptide-stabilized GNP is 8.7 +/- 2.3 nm. Tripeptide bound gold nanoparticles formed three-dimensional assemblies in the presence of an excess of similar or disimilar tripeptides. The aggregation of GNPs results in a red shift in the surface plasmon resonance from lambda max = 527 to 556 nm. The effect of the solvent, concentration, and nature of the tripeptides on the assembly process were investigated by TEM and UV-visible spectroscopy.     

纳米金/单壁碳纳米管复合物的制备、表征及其多相催化的潜力

制备了一种单壁碳纳米管担载金纳米颗粒复合材料,利用X射线衍射、扫描透射显微镜、能量色散X射线分析、比表面积分析、激光拉曼光谱和紫外-可见分光光度计等对其结构进行了表征.结果表明:纳米金粒为微晶体,其平均直径为7nm且直径分布范围较窄.研究了该单壁碳纳米管担载金颗粒对仲醇的无溶剂氧化的活性和选择性,发现其转化效率可达95％.     

Anatase–CMK-3 nanocomposite development for hydrogen uptake and storage

The nanometric carbon CMK-3 modified with TiO₂ in anatase phase was synthesized and applied to energy uptake and storage. TiO₂ nanoclusters are important for hydrogen energy harvesting. The creation of porous structures or large surface with TiO₂ nanoclusters inside can potentially face the challenge of improving their efficiency. In the present work, we report the synthesis and characterization of TiO₂–CMK-3 material assembled from anatase nanoparticles dispersed in the nanometric carbon CMK-3. The resulting nanocomposite was characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy and N₂ adsorption–desorption analysis. The newly synthesized hybrid composites exhibited significantly enhanced H₂ storage, in which CMK-3-ordered porous carbon modified with anatase nanoclusters proved to be a material for hydrogen uptake. The nanoparticles of anatase (～5 nm) incorporated onto CMK-3 showed higher hydrogen uptake at low and high pressures (2.9 wt% of H₂ sorption at 10 bar and 77 K) than CMK-3. The approach includes a discussion of H₂ adsorption process and storage properties.     

Gold-coated magnetic particles for solid-phase immunoassays: enhancing immobilized antibody binding efficiency and analytical performance

The preparation and characterization of gold-coated magnetic particles are described for use as more efficient solid-phase materials in immunoassay development. A thin gold coating on commercial tosylated magnetic polystyrene particles (4.5 microm) is achieved via an electroless plating method involving initial reaction of the particles with Sn(II), followed by redox deposition of Ag0, that serves as a catalytic site for the subsequent reduction of Na3Au(SO3)2 in the presence of formaldehyde to yield the adhered gold layer. Scanning electron microscopy, energy-dispersive X-ray analysis, and X-ray photoelectron spectroscopy indicate the presence of the desired Au0 outer layer. To characterize the improved yield of antibody binding sites on such gold-coated phases, the modified particles are reacted with the free thiols of Fab' fragments of an anti-alkaline phosphatase (ALP) antibody to orient all the antigenic binding sites in a favorable direction. After equilibration with ALP, the amount of ALP bound to the surface of such particles is nearly 2.5-fold greater than on non-gold-coated particles possessing the same amount of immobilized anti-ALP Fab', but oriented randomly on the surface. The new gold-coated magnetic particles are further used as a solid phase for developing a sandwich-type enzyme immunoassay to detect C-reactive protein (CRP) using horseradish peroxidase as the enzyme label. The gold-coated magnetic particles with anti-CRP monoclonal Fab' reagents provide assays with enhanced assay slope (1.8-fold), lower nonspecific adsorption, and a detection limit improvement of nearly 10-fold (0.14 vs 1.9 ng/mL) compared to the same Fab' anti-CRP immobilized on the initial tosylated polystyrene magnetic particles. The improved assay performance is attributed to the more favorable binding orientation of the self-assembled monolayer of Fab' fragments on the gold-coated particles compared to the random orientation on the non-gold-coated surfaces.     

Electroanalytical performance of carbon films with near-atomic flatness

Physicochemical and electrochemical characterization of carbon films obtained by pyrolyzing a commercially available photoresist has been performed. Photoresist spin-coated on to a silicon wafer was pyrolyzed at 1,000 degrees C in a reducing atmosphere (95% nitrogen and 5% hydrogen) to produce conducting carbon films. The pyrolyzed photoresist films (PPF) show unusual surface properties compared to other carbon electrodes. The surfaces are nearly atomically smooth with a root-mean-square roughness of <0.5 nm. PPF have a very low background current and oxygen/carbon atomic ratio compared to conventional glassy carbon and show relatively weak adsorption of methylene blue and anthraquinone-2,6-disulfonate. The low oxygen/carbon ratio and the relative stability of PPF indicate that surfaces may be partially hydrogen terminated. The pyrolyzed films were compared to glassy carbon (GC) heat treated under the same conditions as pyrolysis to evaluate the electroanalytical utility of PPF. Heterogeneous electron-transfer kinetics of various redox systems were evaluated. For Ru(NH3)6(3+/2+), Fe(CN)6(3-/4-), and chlorpromazine, fresh PPF surfaces show electron-transfer rates similar to those on GC, but for redox systems such as Fe3+/2+, ascorbic acid, dopamine, and oxygen, the kinetics on PPF are slower. Very weak interactions between the PPF surface and these redox systems lead to their slow electron-transfer kinetics. Electrochemical anodization results in a simultaneous increase in background current, adsorption, and electron-transfer kinetics. The PPF surfaces can be chemically modified via diazonium ion reduction to yield a covalently attached monolayer. Such a modification could help in the preparation of low-cost, high-volume analyte-specific electrodes for diverse electroanalytical applications. Overall, pyrolysis of the photoresist yields an electrode surface with properties similar to a very smooth version of glassy carbon, with some important differences in surface chemistry.