Gold nanostructures on chemically reinforced PDMS microwell arrays

This paper describes a facile strategy for fabricating arrays of two- and three-dimensional gold nanostructures using PDMS-infiltrated polystyrene (PS) colloidal crystals. PDMS molding of colloidal crystal, gold vapor deposition, and subsequent calcination of PS produced gold thin layers over hexagonal PDMS microwell arrays with hemispherical air-voids of approximately 140 nm on glass substrates. Vapor deposition of perfluoroalkylsilane thin layers improved the thermal stability of the colloidal template over 100 °C, providing a route to preparation of hollow architectures with gold thin layers supported by PDMS nanostructures. Surface modification of the PDMS using poly(allylamine hydrochloride) induced two-dimensional colloidal crystals of PS and PMMA spheres through electrostatic interactions. Particle aggregation of 13 nm gold nanoparticles in the PDMS microwells demonstrated a surface plasmon resonance band red-shifted to 810 nm, in comparison with that on the flat surface at 720 nm.     

桑色素修饰金纳米粒子自组装膜的制备及其性能研究

采用水相硅烷化方法,将γ-氨基丙基三乙氧基硅烷[H₂N(CH₂)₃Si(OC₂H₅)₃](APES)组装在石英表面,在基底表面修饰上氨基为末端的单层膜,并进一步在这种功能化的单层膜基底上组装金纳米粒子得到金纳米粒子/APES/石英的纳米复合结构。以制备的金纳米粒子自组装膜修饰石英为基底及DL-半胱胺酸为中介,利用桑色素(Morin)和DL-半胱胺酸的化学吸附作用,将桑色素间接组装在金纳米粒子自组装膜修饰石英基底表面,所构建的桑色素修饰金纳米粒子自组装膜对三苯基锡有灵敏的荧光识别作用。文章着重研究了桑色素修饰金纳米粒子自组装膜的制备以及组装条件对其荧光行为的影响,探讨了膜的响应特性及响应机理。     

Direct measurement of electron transport features in cytochrome c via V–I characteristics of STM currents

The morphology of and electron tunneling through single and cluster cytochrome c molecules deposited on self-assembled dodecanthiol monolayer film on a gold substrate have been studied experimentally using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy. STM images of a single cytochrome c molecule revealed a globular structure with a diameter of 4 nm and height of 1.5 nm. A spectroscopic study obtained by recording tunneling current–bias voltage (V–I) curves revealed that the STM current increases stepwise at asymmetric threshold sample bias voltages of +100 mV and –200 mV.     

Au标蛋白自组装表面增强拉曼光谱的研究

采用免疫Au标技术,用尺寸大约在13 nm的Au胶体颗粒标记了人血清蛋白(Human IgG),然后将Au标蛋白复合体固定在通过三氨基三乙氧基硅烷和戊二醛自组装单膜的Si片上。这种方法在基底表面上不仅牢固地固定了单层Au纳米颗粒标记的蛋白分子复合体而且提高了复合体的表面覆盖度,保持了生物分子的结构。利用原子力显微镜(AFM)观察了Au标蛋白的自组装表面。实验结果表明Au标蛋白在Si片表面聚积形成一定的Au标蛋白分子的复合体“岛状”单层,并且在这些岛状单层上获得了很明显的标记蛋白的表面增强拉曼散射(SERS)信号。文章在Si表面自组装了Au标蛋白分子,获得了较好的蛋白分子的SERS信号,提供了一种研究蛋白分子的SERS活性基底。     

Extracellular biosynthesis of monodispersed gold nanoparticles by a SAM capping route

Monodispersed gold nanoparticles capped with a self-assembled monolayer of dodecanethiol were biosynthesized extracellularly by an efficient, simple, and environmental friendly procedure, which involved the use of Bacillus megatherium D01 as the reducing agent and the use of dodecanethiol as the capping ligand at 26 °C. The kinetics of gold nanoparticle formation was followed by transmission electron microscope (TEM) and UV-vis spectroscopy. It was shown that reaction time was an important parameter in controlling the morphology of gold nanoparticles. The effect of thiol on the shape, size, and dispersity of gold nanoparticles was also studied. The results showed that the presence of thiol during the biosynthesis could induce the formation of small size gold nanoparticles (<2.5 nm), hold the shape of spherical nanoparticles, and promote the monodispersity of nanoparticles. Through the modulation of reaction time and the use of thiol, monodispersed spherical gold nanoparticles capped with thiol of 1.9 ± 0.8 nm size were formed by using Bacillus megatherium D01.     

Peptide-induced patterning of gold nanoparticle thin films

In this work, the use of patterned proteins and peptides for the deposition of gold nanoparticles on several substrates with different surface chemistries is presented. The patterned biomolecule on the surface acts as a catalyst to precipitate gold nanoparticles from a precursor solution of HAuCl₄ onto the substrate. The peptide patterning on the surfaces was accomplished by physical adsorption or covalent attachment. It was shown that by using covalent attachment with a linker molecule, the influence of the surface properties from the different substrates on the biomolecule adsorption and subsequent nanoparticle deposition could be avoided. By adjusting the reaction conditions such as pH or HAuCl₄ concentration, the sizes and morphologies of deposited gold nanoparticle agglomerates could be controlled. Two biomolecules were used for this experiment, 3XFLAG peptide and bovine serum albumin (BSA). A micro-transfer molding technique was used to pattern the peptides on the substrates, in which a pre-patterned poly(dimethylsiloxane) (PDMS) mold was used to deposit a lift-off pattern of polypropylmethacrylate (PPMA) on the various substrates. The proteins were either physically adsorbed or covalently attached to the substrates, and an aqueous HAuCl₄ solution was applied on the substrates with the protein micropatterns, causing the precipitation of gold nanoparticles onto the patterns. SEM, AFM, and Electron Beam Induced Current (EBIC) were used for characterization.     

Sub-micron scale patterning using femtosecond laser and self-assembled monolayers interaction

Standard positive photoresist techniques were adapted to generate sub-micron scale patterns of gold substrate using self-assembled monolayers (SAMs) and femtosecond laser. Self-assembled monolayers formed by the adsorption of alkanethiols onto gold substrate are employed as very thin photoresists. The process underlying photopatterning of SAMs on gold is well-known at the phenomenological level. Alkanethiolates formed by the adsorption of alkanethiols are oxidized on exposure to UV light in the presence of air to alkylsulfonates. Specifically, it is known that deep UV light of wavelength less than 200 nm is necessary for oxidation to occur. In this study, solid state femtosecond laser of wavelength 800 nm is applied for photolithography. The results show that ultrafast laser of near infrared (NIR) range wavelength can replace deep UV laser source for photopatterning using thin organic films. The essential basis of our approach is the photochemical excitation of specific reactions in a particular functional group (in this case a thiolate sulfur atom) distributed with monolayer coverage on a solid surface. Femtosecond laser photolithography could be applied to fabricate the patterning of surface chemical structure and the creation of three-dimensional nanostructures by combination with suitable etching methods.     

CdS纳米粒子的自组装单分子膜制备研究

利用疏基乙酸与草酸的混合自组装单分子膜成功制备了粒径分布均匀的CdS纳米粒子，并用SEM，XRD，XPS，PL对样品进行了表征。SEM表明形成在自组装单分子膜表面上的CdS纳米粒子的平均粒径约为45nm。XPS表明在自组装单分子膜表面形成了CdS纳米粒子。PL谱表明CdS纳米粒子在675nm有一峰值波长，我们认为这一发光是由表面缺陷造成的。     

The formation of sub-10 nm nanohole array on block copolymer thin films on gold surface using surface neutralization based on O2 plasma treatment and self-assembled monolayer

Blockcopolymer (BCP) lithography is an emerging nanolithography technique for fabrications of various nanoscale devices and materials. In this study, self-assembled BCP thin films having cylindrical nanoholes were prepared on gold by surface neutralization using self-assembled monolayer (SAM). Oxygen plasma treatment was investigated as a way to enhance the functionality of Au surface toward SAM formation. After surface neutralization, well-ordered nanoholes with 9 to 20 nm diameters were formed inside BCP thin films on Au surfaces through microphase separation. The effects of oxygen plasma treatment on the formation of BCP nanopattern were investigated using surface analysis techniques including X-ray photoelectron spectroscopy (XPS) and water contact angle measurement. Au nanodot arrays were fabricated on gold film by utilizing the BCP nanotemplate and investigated by atomic force microscopy (AFM).     

Enhanced dispersion and stability of gold nanoparticles on stoichiometric and reduced TiO2(1 1 0) surface in the presence of molybdenum

Mo, Au and their coadsorbed layers were produced on nearly stoichiometric and oxygen-deficient titania surfaces by physical vapor deposition (PVD) and characterized by low energy ion scattering (LEIS), X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and scanning tunnelling microscopy (STM). The behavior of Au/Mo bimetallic layers was studied at different relative metal coverages and sample temperatures.

STM data indicated clearly that the deposition of Au on the Mo-covered stoichiometric TiO₂(1 1 0) surface results in an enhanced dispersion of gold at 300 K. The mean size of the Au nanoparticles formed at 300 K on the Mo-covered TiO₂(1 1 0) was significantly less than on the Mo-free titania surface (2 ± 0.5 nm and 4 ± 1 nm, respectively). Interestingly, the deposition of Mo at 300 K onto the stoichiometric TiO₂(1 1 0) surface covered by Au nanoparticles of 3–4 nm (0.5 ML) also resulted in an increased dispersity of gold. The driving force for the enhanced wetting at 300 K is that the Au–Mo bond energy is larger than the Au–Au bond energy in 3D gold particles formed on stoichiometric titania. In contrast, 2D gold nanoparticles produced on ion-sputtered titania were not disrupted in the presence of Mo at 300 K, indicating a considerable kinetic hindrance for breaking of the strong Au-TiO_x bond.

The annealing of the coadsorbed layer formed on a strongly reduced surface to 740 K did not cause a decrease in the wetting of titania surface by gold. The preserved dispersion of Au at higher temperatures is attributed to the presence of the oxygen-deficient sites of titania, which were retained through the reaction of molybdenum with the substrate. Our results suggest that using a Mo-load to titania, Au nanoparticles can be produced with high dispersion and high thermal stability, which offers the fabrication of an effective Au catalyst.     

Trapping and release of citrate-capped gold nanoparticles

An electrical method to trap and release charged gold nanoparticles onto and from the surface of gold electrodes modified by an alkanethiol self-assembled monolayer (SAM) is presented. To form electrodes coated with gold nanoparticles (GNPs), amine-terminated SAMs on gold electrodes were immersed in a solution of negatively charged citrate-capped GNPs. Accumulation of GNPs on the electrode surface was monitored by a decrease in the impedance of the SAM-modified electrode and by an increase in the electrochemical activity at the electrode as shown through cyclic voltammetry (CV). Electrostatic interactions between the GNPs and the amine-terminated SAM trap the GNPs on the electrode surface. Application of a subsequent negative bias to the electrode initiated a partial release of the GNPs from the electrode surface. Impedance spectroscopy, cyclic voltammetry, ultraviolet-visible (UV-Vis) spectroscopy and atomic force microscopy (AFM) were used to monitor and confirm the attraction of GNPs to and release from the aminealkanethiolated gold electrodes. This work describes a method of trapping and release for citrate-capped GNPs that could be used for on-demand nanoparticle delivery applications such as in assessing and modeling nanoparticle toxicology, as well as for monitoring the functionalization of gold nanoparticles.     

金纳米空心半球壳膜的可调谐光学性质研究

以单层聚苯乙烯微球阵列为模板,通过控制其表面金膜蒸镀时间,制备了具有不同厚度的空心半球壳结构的金纳米膜.利用扫描电子显微镜和自制光谱仪分别测量了金膜表面形貌和其透射光谱,并分析了金膜形貌与其光学性质间的关系,同时以4-巯基苯胺为探针分子测定了金膜的表面增强喇曼散射效应.结果表明,该金纳米膜的表面等离子体共振波长随膜厚度增大而发生红移,在可见与近红外波段较宽范围内可调谐,并且,当金膜共振波长与入射激发光波长较近时,探针分子可产生出较强的表面增强喇曼信号.同时,对该现象的产生机制也进行了理论解释.     

Adhesion of chemically and electrostatically bound gold nanoparticles to a self-assembled silane monolayer investigated by atomic force volume spectroscopy

The adhesion of gold nanoparticles either electrostatically or chemically attached to a substrate has been probed using AFM operating in force spectroscopy mode. A monolayer of –NH₂ terminated 3-aminopropyltriethoxysilane or –SH terminated 3-mercaptopropyltrimethoxysilane was self-assembled onto a p-type silicon (100) substrate. Each silane monolayer provided the point of attachment for citrate stabilised gold colloid nanoparticles. In the case of the –NH₂ terminated layer gold colloid assembly was driven by the electrostatic attraction between the negative, citrate-capped, gold nanoparticles and a partially protonated amine layer. In the case of the –SH terminated regions, well-known gold–thiol chemistry was used to chemically attach the nanoparticles. An atomic force microscope tip was chemically modified with 3-mercaptopropyltrimethoxysilane and scanned across each surface, where the cantilever deflection was measured at each x, y pixel of the image to create an array of adhesion force curves. This has allowed an unprecedented nanoscale characterisation of the adhesion force central to two common surface attachment methods of gold colloid nanoparticles, providing useful insights into the stability of nanoscale constructs.     

Nanoindentation of gold nanoparticles functionalized with proteins

The hardness and Young's modulus of 10 and 20 nm gold nanoparticles (Au NPs) modified with bovine serum albumin and streptavidin were measured using a nanoindenter. The Au NPs were immobilized on a semiconductor surface through organic self-assembled monolayers. Changes in mechanical properties occurred when the Au NPs were immobilized on the surface. The hardness and Young's modulus were dependent on the size of the NPs, and the proteins on the particles showed highly plastic and elastic behavior compared to flat surfaces modified with self-assembled monolayers.     

Nanostructures of gold coated iron core-shell nanoparticles and the nanobands assembled under magnetic field

Pure metal iron nanoparticles are unstable in the air. By a coating iron on nanoparticle surface with a stable noble metal, these air-stable nanoparticles are protected from the oxidation and retain most of the favorable magnetic properties, which possess the potential application in high density memory device by forming self-assembling nanoarrays. Gold-coated iron core-shell structure nanoparticles (Fe/Au) synthesized using reverse micelles were characterized by transmission electron microscopy (TEM). The average nanoparticle size of the core-shell structure is about 8 nm, with about 6 nm diameter core and 1∼2 nm shell. Since the gold shell is not epitaxial growth related to the iron core, the morié pattern can be seen from the overlapping of iron core and gold shell. However, the gold shell lattice can be seen by changing the defocus of TEM. An energy dispersive X-ray spectrum (EDS) also shows the nanoparticles are air-stable. The magnetic measurement of the nanoparticles also proved successful synthesis of gold coated iron core-shell structure. The nanoparticles were then assembled under 0.5 T magnetic field and formed parallel nanobands with about 10 μm long. Assembling two dimensional ordered nanoarrays are still under going. Received 29 November 2000     

Synthesis and physico-chemical characteristics of nanosized particles produced by laser ablation of a nickel target in water

Ablation of Ni targets in water by laser impact (532 nm, 40 mJ/pulse, 10 Hz and 8 ns duration) focused on massive samples (2 mm diameter) generates colloids with fine nanoparticles. The amount of metal released in the solution (measured by mass loss of the target or ICP) was found to increase first linearly with time, but slower after 8 min of impact. The size distribution of the nanoparticles thus produced was measured (by TEM) to be in the range 3–5.3 nm in diameter, with a tendency for the size to be smaller for larger number of laser shots. Actually, nickel oxide nanoparticles were produced, rather than nickel nanoparticles as it was shown by HRTEM. XPS photoemission measurements evidenced the presence of nickel oxide species on the crater of the nickel sample surface after laser ablation.     

Degradation of octanethiol self-assembled monolayers from hydrogen-atom exposure: A molecular-scale study using scanning tunneling microscopy

Octanethiol self-assembled monolayers were exposed to gas-phase hydrogen atoms, and the resulting changes in the order and chemical structure of the surface were monitored using scanning tunneling microscopy (STM). Extensive damage to the monolayer was observed in the form of both dark and bright features in STM images. These changes began along domain boundaries and moved into close-packed regions of the monolayer as hydrogen-atom exposure time increased. Increasing exposure also results in an accelerated rate of observed surface changes, indicating that the reactivity of the surface increases as a result of initial gas-surface reactions. Complex restructuring of the alkanethiol monolayer is observed, including defect formation and the disordering of the alkanethiol monolayer. However, in some cases the monolayer demonstrates the capability of self-healing, with local annealing and reordering of close-packed domains. This annealing and reordering likely results from increased mobility of surface-bound alkanethiolates in the vicinity of monolayer defects, or from diffusion and readsorption of transiently formed alkanethiol molecules.     

Direct observation of slow morphological transformations and wetting behavior of pulsed laser deposited sub-monolayer gold on (0 0 0 1) sapphire in atmosphere

Using high-resolution atomic force microscope we observed in ambient atmosphere the slow morphological transitions of the incipient adlayer of gold grown on (0 0 0 1) sapphire substrate by pulsed laser deposition. The equivalent average uniform thickness of the gold deposition was about 0.55 Å, which is about one-fourth of its monolayer. A dynamic simulation revealed that about 10% of the gold was implanted into the substrate up to the depth of about 3.3 nm and the top monolayer of the sapphire surface was almost completely depleted of oxygen atoms due to the preferential sputtering by the plume particles. The gold adlayer transformed into a labile phase which enhanced the surface roughness and had a preferred orientation of a wavy structure during 24 h of the deposition. The auto-correlation function of this wavy structure in labile metastable phase revealed two-fold symmetry and provided a preferential size of about 4 nm (peak to peak) with a mean separation of 8 nm. At the end of about 6 days this phase was found to completely transform into an apparently de-wetted phase of beads with average in-plane diameter of ∼20 nm and height of ∼7 nm having large size distribution. Each bead was seen to have coating of a concentric corona layer, which might be that of the condensed moisture or other gaseous species from atmosphere because subjecting these samples to vacuum removed this layer. These observations shed light on the dynamics of the pulsed laser deposited metastable gold adlayer in the incipient stage of its growth on sapphire and their wetting or de-wetting mechanisms in ambient atmosphere.     

对氨基苯甲酸在不同基底上的SERS研究

用氢气还原氧化银的方法合成了粒径约为100nm的银纳米粒子,然后在表面经PVP修饰的载玻片上以自组装的方式构筑了银纳米粒子单层和双层二维有序阵列,在铝基底上通过对氨基苯甲酸成功构筑了银纳米粒子的有序组装体,用扫描电镜进行了表征;对不同基底二维有序阵列的表面增强拉曼光谱进行了研究,结果表明,对氨基苯甲酸在银和铝基基底上都是垂直吸附,其表面拉曼增强效应是电磁场增强占主导地位,但同时也有化学增强的贡献。     

Rapid extra-/intracellular biosynthesis of gold nanoparticles by the fungus <Emphasis Type="Italic">Penicillium</Emphasis> sp.

In this work, the fungus Penicillium was used for rapid extra-/intracellular biosynthesis of gold nanoparticles. AuCl₄ ⁻ ions reacted with the cell filtrate of Penicillium sp. resulting in extracellular biosynthesis of gold nanoparticles within 1 min. Intracellular biosynthesis of gold nanoparticles was obtained by incubating AuCl₄ ⁻ solution with fungal biomass for 8 h. The gold nanoparticles were characterized by means of visual observation, UV–Vis absorption spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDX). The extracellular nanoparticles exhibited maximum absorbance at 545 nm in UV–Vis spectroscopy. The XRD spectrum showed Bragg reflections corresponding to the gold nanocrystals. TEM exhibited the formed spherical gold nanoparticles in the size range from 30 to 50 nm with an average size of 45 nm. SEM and TEM revealed that the intracellular gold nanoparticles were well dispersed on the cell wall and within the cell, and they are mostly spherical in shape with an average diameter of 50 nm. The presence of gold was confirmed by EDX analysis.