Incorporation of surface-derivatized gold nanoparticles into electrochemically generated polymer films

Stable colloidal solutions of gold nanoparticles surface-derivatized with a thiol monolayer have been prepared using two-phase (water–nitrobenzene) reduction of AuCl₄⁻ by sodium borohydride in the presence of 2-mercapto-3-n-octylthiophene (MOT). This kind of surface-functionalized gold nanoparticles can be easily incorporated into the poly(3-octylthiophene) (POT) films on electrode in the process of electrochemical polymerization leading to POT–gold nanoparticle (POT–Au) composite films. Scanning probe microscopy (SPM) and X-ray photoelectric spectroscopy (XPS) have been employed to characterize the surface-derivatized particles and the resulting films. The method of incorporation of nanoparticles into polymer by surface-derivatization and in situ polymerization can also be employed to prepare many other polymer–nanoparticle compostie materials.     

Au@PS纳米颗粒掺杂PDMS/(PVDF-TrFE)复合薄膜的制备及介电-疏水性能

结合乳液聚合和还原法在250 nm的聚苯乙烯(PS)微球表面均匀负载了Au纳米颗粒.通过溶液共混法,使Au@PS纳米颗粒与聚二甲基硅氧烷(PDMS)/聚偏氟乙烯-三氟乙烯[P(VDF-TrFE)](质量比为2∶3)均匀混合,制备出结构致密、Au@PS均匀分布的微突起的复合薄膜.研究了不同Au@PS纳米颗粒掺杂量对复合薄膜的结构、熔融结晶行为和介电疏水特性的影响.研究发现,Au@PS纳米颗粒的引入阻碍了P(VDFTr FE)的β相的产生,但对PDMS/P(VDF-TrFE)复合薄膜的化学健结构没有显著影响;随着Au@PS纳米颗粒含量的增多,复合薄膜结晶温度和玻璃化转化温度升高,熔点略有降低.由于界面极化和微电容效应协同作用,掺杂Au@PS复合薄膜的介电常数有显著提升.PS球表面均匀负载的Au纳米颗粒减少了导电网络的构成,使介电损耗维持在较低值.掺杂5%(质量分数) Au@PS的复合薄膜介电常数达到22(100 Hz),分别为纯PDMS和PDMS/P(VDF-TrFE)的8. 8倍和3. 14倍,同时具有优异的疏水特性,接触角达到112. 31°.     

Aerosol assisted chemical vapor deposition using nanoparticle precursors: a route to nanocomposite thin films

Gold nanoparticle and gold/semiconductor nanocomposite thin films have been deposited using aerosol assisted chemical vapor deposition (CVD). A preformed gold colloid in toluene was used as a precursor to deposit gold films onto silica glass. These nanoparticle films showed the characteristic plasmon absorption of Au nanoparticles at 537 nm, and scanning electron microscopic (SEM) imaging confirmed the presence of individual gold particles. Nanocomposite films were deposited from the colloid concurrently with conventional CVD precursors. A film of gold particles in a host tungsten oxide matrix resulted from co-deposition with [W(OPh)(6)], while gold particles in a host titania matrix resulted from co-deposition with [Ti(O(i)Pr)(4)]. The density of Au nanoparticles within the film could be varied by changing the Au colloid concentration in the original precursor solution. Titania/gold composite films were intensely colored and showed dichromism: blue in transmitted light and red in reflected light. They showed metal-like reflection spectra and plasmon absorption. X-ray photoelectron spectroscopy and energy-dispersive X-ray analysis confirmed the presence of metallic gold, and SEM imaging showed individual Au nanoparticles embedded in the films. X-ray diffraction detected crystalline gold in the composite films. This CVD technique can be readily extended to produce other nanocomposite films by varying the colloids and precursors used, and it offers a rapid, convenient route to nanoparticle and nanocomposite thin films.     

3-Glycidoxypropyltrimethoxysilane mediated in situ synthesis of noble metal nanoparticles: application to hydrogen peroxide sensing

The in situ synthesis is reported of noble metal nanoparticles via 3-glycidoxypropyltrimethoxysilane mediated reduction of 3-aminopropyltrimethoxysilane treated metal salts during sol-gel processing. The method described involves the synthesis of uniform spherical nanoparticles of gold, silver and palladium with controlled size that can be directly utilized for thin film preparation. A detailed study of the synthesis and application of gold nanoparticles to the electrochemical detection of hydrogen peroxide was carried out and reveals that the amplification of hydrogen peroxide sensing is size-dependent. In addition, these nanoparticles exhibit excellent compatibility towards composite preparation. As an example, a nanocomposite with Prussian Blue (PB) is synthesized and found to be useful for the fabrication of chemically modified electrodes (CME). The resulting CME shows dramatic improvement in the electrochemistry of PB with gradual enhancement in electrocatalytic efficiency towards hydrogen peroxide sensing. The nanocomposite is used to study the direct and horseradish peroxidase (HRP)-catalyzed reduction of hydrogen peroxide. The results recorded for hydrogen peroxide analysis show an improvement in sensitivity and limit of detection on decreasing the size of gold nanoparticles in all cases.     

基于粒子辅助水滴模板法制备仿生复眼结构的研究

将微粒“皮克林乳化效应”(Pickering emulsions)和水滴模板法(breath figure method)有机结合,探索通过建立粒子辅助的水滴模板法,实现纳米粒子在蜂窝状多孔膜内壁的自组装复合,构建微纳复合的多级仿生结构.并进一步利用聚二甲基硅氧烷(PDMS)复制转移技术,获得类似于复眼结构的多级微纳复合界面仿生结构.     

Substrate- and time-dependent photoluminescence of quantum dots inside the ultrathin polymer LbL film

The photoluminescence of CdSe/ZnS quantum dots (QDs) in different configurations at solid surfaces (glass, silicon, PDMS, and metals) is considered for three types of organization: QDs directly adsorbed on solid surfaces, separated from the solid surface by a nanoscale polymer film with different thickness, and encapsulated into a polymer film. The complete suppression of photoluminescence for QDs on conductive metal surfaces (copper, gold) indicated a strong quenching effect. The temporal variation of the photoluminescent intensity on other substrates (glass, silicon, and PDMS) can be tuned by placing the nanoscale (3-50 nm) LbL polymer film between QDs and the substrate. The photooxidation and photobleaching processes of QD nanoparticles in the vicinity of the solid surface can be tuned by proper selection of the substrate and the dielectric nanoscale polymer film placed between the substrate and QDs. Moreover, the encapsulation of QD nanoparticles into the polymer film resulted in a dramatic initial increase in the photoemission intensity due to the accelerated photooxidation process. The phenomenon of enhanced photoemission of QDs encapsulated into the ultrathin polymer film provides not only the opportunity for making flexible, ultrathin, QD-containing polymer films, transferable to any microfabricated substrate, but also improved light emitting properties.     

Synthesis and structure of poly-3,4-ethylenedioxythiophene film with the inclusions of palladium nanoparticles

By chemical deposition of ultrafine particles of metallic palladium on the polymer matrix of poly-3,4-ethylenedioxythiophene (PEDOT) composite PEDOT/Pd films were obtained. The conditions of synthesis of the composite films in dependence on the duration of exposure of the reduced form of PEDOT film in a solution of palladium chloride, its concentration and the film thickness were studied. By the methods of scanning electron microscopy (SEM) and transmission electron microscopy (TEM) it was shown that in the process of the synthesis of the composite films the nanosized palladium particles of predominantly quasispherical shape precipitated on the globular structure of the polymer. The size of the palladium nanoparticles in the composite PEDOT film and the nature of their distribution over the film bulk were revealed. An increase in the duration of deposition of the palladium nanoparticles on the film was shown to lead to an increase in their size and in the density of particles in the film.     

Silver and gold nanoparticles in silica matrices: synthesis,properties, and application

Methods of synthesis, optical characteristics, morphology, and catalytic and bactericidal characteristics of composite materials based on silica (films and powders) containing nanoparticles of silver, gold, and their binary compounds with alloy or core–shell structure are examined. The photochemical reduction of Au³⁺ and Ag⁺ with a photocatalyst (a film of SiO₂ with adsorbed benzophenone) makes it possible to generate stable nanoparticles of gold and silver in solutions for subsequent introduction into adsorbents and catalysts. Examples of the use of nanosized composites in catalysis and in microbiological experiments are presented.     

Stability and Morphology of Gold Nanoisland Arrays Generated from Layer-by-Layer Assembled Nanoparticle Multilayer Films: Effects of Heating Temperature and Particle Size

This article reports the effects of heating temperature and composition of nanoparticle multilayer films on the morphology, stability, and optical property of gold nanoisland films prepared by nanoparticle self-assembly/heating method. First, nanoparticle-polymer multilayer films are prepared by the layer-by-layer assembly. Nanoparticle multilayer films are then heated at temperature ranging from 500 °C to 625 °C in air to induce an evaporation of organic matters from the films. During the heating process, the nanoparticles on the solid surface undergo coalescence, resulting in the formation of nanostructured gold island arrays. Characterization of nanoisland films using atomic force microscopy and UV-vis spectroscopy suggests that the morphology and stability of gold island films change when different heating temperatures are applied. Stable gold nanoisland thin film arrays can only be obtained after heat treatments at or above 575 °C. In addition, the results show that the use of nanoparticles with different sizes produces nanoisland films with different morphologies. Multilayer films containing smaller gold nanoparticles tend to produce more monodisperse and smaller island nanostructures. Other variables such as capping ligands around nanoparticles and molecular weight of polymer linkers are found to have only minimal effects on the structure of island films. The adsorption of streptavidin on the biotin-functionalized nanoisland films is studied for examining the biosensing capability of nanoisland arrays.     

三氧化钼与金纳米粒子复合薄膜光致变色特性的研究

MoO3具有光致变色特性,在大屏幕显示、高密度存储和灵巧窗等研究领域中具有潜在的应用前景^[1-3]。但由于MoO3薄膜中相当一部分光生载流子被复合,其参与变色反应的利用率很低,导致MoO3薄膜的变色效率较低,使其难以实现实用化。半导体表面修饰贵金属后,在半导体／金属界面上可形成Schottky势垒,这将有助于光生载流子的有效分离,从而提高其利用率。据此,本文采用在MoO3薄膜表面修饰金纳米粒子的方法,制备了MnO3和金纳米粒子的复合薄膜（MoO3/Au),变色试验结果表明,MoO3/Au复合薄膜的紫外和可见光变色效率相对MoO3薄膜均有较大的提高。     

Surface modification with BSA blocking based on in situ synthesized gold nanoparticles in poly(dimethylsiloxane) microchip

A stable BSA blocking poly(dimethylsiloxane) (PDMS) microchannel was prepared based on in situ synthesized PDMS–gold nanoparticles composite films. The modified microchip could successfully suppress protein adsorption. The assembly was followed by contact angle, charge-coupled device (CCD) imaging, electroosmotic flow (EOF) measurements and electrophoretic separation methods. Contact angle measurements revealed the coated surface was hydrophilic, water contact angle for coated chips was 45.2° compared to a water contact angle for native PDMS chips of 88.5°. The coated microchips exhibited reproducible and stable EOF behavior. With FITC-labeled myoglobin incubation in the coated channel, no fluorescence was observed with CCD image, and the protein exhibited good electrophoretic effect in the modified microchip.     

Gold electroless deposition into poly-3,4-ethylenedioxythiophene films

By electroless deposition of gold into poly-3,4-ethylenedioxythiophene (PEDOT) films, the composite films (PEDOT-Au) are synthesized. Their electrochemical properties are studied by cyclic voltammetric (CVA) method. It is shown that in contrast to the original PEDOT film, the CVA curves of composite PEDOT-Au films measured in the presence of chloride ions reveal additional redox peaks associated with the presence of gold particles. The loading of metal gold particles by its chemical deposition into the polymer film is quantitatively assessed using quartz crystal microbalance method. The film mass is shown to depend on the time of gold loading and its original concentration in solution. The gold particles are shown to be oxidized by a reaction of the first order with respect to chloride ions. Based on the results of voltammetric and microbalance methods, the formation of a poorly soluble gold oxidation product Au(I)Cl in chloride-containing solutions was inferred.     

Mechanism of a microwave-assisted polyol synthesis of nanosize CuInSe2 particles and their optical and photoelectric properties

Mechanism of the reaction in which CuInSe₂ nanoparticles are formed in synthesis by the microwaveassisted polyol method was studied. The morphology and optical properties of thin layers (films) produced from the synthesized CuInSe₂ nanoparticles and the morphology and photoelectric properties of composite films based on CuInSe₂ and [6,6]phenyl C61 butyric acid methyl ester were examined. It is shown that CuInSe₂ nanoparticles can be used to form a photo-absorbing layer in composite organo-inorganic solar cells.     

卟啉铜/CdSe纳米粒子复合膜的组装及其光学性能

采用静电自组装的方法,将带有相反电荷的水溶性卟啉--碘化三甲胺基苯基卟啉铜与CdSe纳米粒子交替沉积,制备了一种新型的有机-无机纳米复合薄膜。 紫外-可见吸收光谱表明,复合膜是逐层、均匀沉积的。 扫描电子显微镜照片显示复合膜中纳米粒子分布均匀,膜结构中缺陷少。 此外,还通过光谱手段系统地研究了该复合膜的发光性能、纳米粒子与卟啉之间的相互作用及膜的光稳定性。 研究结果发现,CdSe纳米粒子与CuTAPPI分子之间存在较强的相互作用,能产生由CuTAPPI到CdSe的光诱导电子转移。 而且,在该复合膜中CuTAPPI的光稳定性较高。     

有机溶剂热生长技术制备硫族化合物及其光学特性的研究

以有机溶剂热生长技术(solvothermaltechnique)制备了半导体硫族化合物(CdS、ZnS、MoS₂)等纳米颗粒,采用XRD、TEM等技术对其结构进行表征.以ITO导电玻璃以及导电聚合物(PANI、PPY)膜为基底,将纳米颗粒涂布其上并以PL法研究其光学特性,实验结果表明:经修饰后,材料的荧光发射位置发生显著的变化.     

Immobilization of biogenic gold nanoparticles in thermally evaporated fatty acid and amine thin films

We have recently demonstrated the biological synthesis of gold nanoparticles by the reduction of aqueous chloroaurate ions by the fungus Fusarium oxysporum and with extract of geranium (Pelargonium graveolens) leaf. In this paper, we demonstrate the immobilization of biogenic gold nanoparticles in lipid thin films deposited by thermal evaporation. The charge on the gold nanoparticles synthesized by both the fungus and the geranium plant extract is used to facilitate their immobilization in both anionic and cationic lipid thin films. A rough estimate of the isoelectric point of the proteins capping the gold nanoparticles synthesized using the fungus could be made by pH-dependent microgravimetry studies of the immobilization process. An interesting size and shape selectivity in the immobilized gold nanoparticles is observed in the lipid thin films. The biogenic gold nanoparticle-lipid composite films were characterized using quartz crystal microgravimetry, UV-vis absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and transmission electron microscopy.     

Wrinkles formed on a thin gold film deposited onto stretched elastic substrates

In this article the possibility of using various elastic polymer substrates for preparing wrinkled gold films was studied. The gold film was deposited on the substrate using an ion‐sputtering technique, while the substrate was stretched and fixed on a frame. The obtained gold film had wrinkles with a striped pattern. However, whether the pattern was well regulated or not depended on the substrate material. Polydimethylsiloxane (PDMS) was the preferable material when it did not contain fillers. Materials containing fillers are not suitable for this purpose. However, double layer substrates that consist of the PDMS without fillers (the upper layer) and the material containing fillers (the lower layer) could be used to obtain a relatively well‐ordered pattern. Copyright © 2005 John Wiley & Sons, Ltd.     

Photovoltaic cells using composite nanoclusters of porphyrins and fullerenes with gold nanoparticles

Novel organic solar cells have been prepared using quaternary self-organization of porphyrin (donor) and fullerene (acceptor) units by clusterization with gold nanoparticles on nanostructured SnO2 electrodes. First, porphyrin-alkanethiolate monolayer-protected gold nanoparticles (H2PCnMPC: n is the number of methylene groups in the spacer) are prepared (secondary organization) starting from the primary component (porphyrin-alkanethiol). These porphyrin-modified gold nanoparticles form complexes with fullerene molecules (tertiary organization), and they are clusterized in acetonitrile/toluene mixed solvent (quaternary organization). The highly colored composite clusters can then be assembled as three-dimensional arrays onto nanostructured SnO2 films to afford the OTE/SnO2/(H2PCnMPC+C60)m electrode using an electrophoretic deposition method. The film of the composite clusters with gold nanoparticle exhibits an incident photon-to-photocurrent efficiency (IPCE) as high as 54% and broad photocurrent action spectra (up to 1000 nm). The power conversion efficiency of the OTE/SnO2/(H2PC15MPC+C60)m composite electrode reaches as high as 1.5%, which is 45 times higher than that of the reference system consisting of the both single components of porphyrin and fullerene.     

In situ Synthesis of Metal Nanoparticle Embedded Free Standing Multifunctional PDMS Films

We demonstrate a simple one‐step method for synthesizing noble metal nanoparticle embedded free standing polydimethylsiloxane (PDMS) composite films. The process involves preparing a homogenous mixture of metal salt (silver, gold and platinum), silicone elastomer and the curing agent (hardener) followed by curing. During the curing process, the hardener crosslinks the elastomer and simultaneously reduces the metal salt to form nanoparticles. This in situ method avoids the use of any external reducing agent/stabilizing agent and leads to a uniform distribution of nanoparticles in the PDMS matrix. The films were characterized using UV‐Vis spectroscopy, transmission electron microscopy and X‐ray photoemission spectroscopy. The nanoparticle‐PDMS films have a higher Young's modulus than pure PDMS films and also show enhanced antibacterial properties. The metal nanoparticle‐PDMS films could be used for a number of applications such as for catalysis, optical and biomedical devices and gas separation membranes.

     

Electrochemical synthesis of gold nanocrystals and their 1D and 2D organization

Size-controlled gold nanocrystals were conveniently synthesized through direct electroreduction of bulk AuCl(4)(-) ions in the presence of poly(N-vinylpyrrolidone) (PVP). PVP greatly enhanced the gold particle formation process and also significantly retarded the gold electrodeposition process, allowing the electrochemical synthesis of gold nanocrystals to be carried out in the form of simple electroreduction. This novel electrochemical method may be extended to synthesis of other noble metal nanoparticles with controllable size on a large scale. The PVPK90-protected gold nanocrystals spontaneously self-assembled into nearly ordered 2D close-packed arrays and interesting 1D nanostructures. The aggregation of unstable PVPK17-protected gold nanocrystals resulted in the formation of ultrathin single-crystalline films. PVP plays multifunctional roles in controlling the size and shape of gold nanocrystals and in inducing individual gold nanocrystals to construct 1D nanostructures. The nanoparticle self-assembling technique based on PVP offers a simple, but effective, path to organize individual gold nanoparticles into various 1D and 2D nanostructured materials.