聚苯胺包裹的金纳米粒子的合成和表征及初步应用

用苯胺作还原剂还原氯金酸合成了金纳米结构. TEM实验表明, 苯胺还原氯金酸能生成苯胺齐聚物或其聚合物包裹的金球形纳米粒子. XPS分析表明, 金纳米粒子包覆的聚合物层带正电荷. 该纳米粒子能用于电极表面纳米结构组装及氧化还原性的生物大分子的电化学研究, 实现了超氧化物歧化酶(SOD)在这种带正电荷的金纳米粒子表面的直接电子转移.     

Gold nanoparticle assemblies through hydrogen-bonded supramolecular mediators

The synthesis of spherical gold nanoparticle assemblies with multicomponent double rosette molecular boxes as mediators is presented. These nine-component hydrogen-bonded supramolecular structures held together by 36 hydrogen bonds induce gold nanoparticle assembly. The morphologies of the nanoparticle assemblies can be tuned easily by changing the quantity of the building block chemisorbed on the nanoparticle surface.     

基于AFM纳米氧化技术的金纳米粒子定点组装

二维纳米粒子矩阵列在纳米电子器件^[1,2]、表面增强喇曼活性基底^[3,4]、刻蚀掩模^[5]等领域具有广泛的应用前景。在这些纳米粒子阵列为内部,纳米粒子的排布是随机、无序的。这一缺点已经妨碍了纳米粒子阵列在上述领域中的进一步应用。基于此,人们开始关注纳米粒子的可控组装。传统的光刻技术^[6]、微接触印刷技术^[7]以及生物分子模板技术^[8]都被用来实现纳米粒子在固体表面上的可控组装,本实验室在纳米粒子的合成及可控组装方面也进行了研究^[7,9,11]。本文力图精确控制单个纳米粒子在基底表面上的组装位置。利用AFM纳米氧化技术。在硅表面构建了纳米级的化学图形化表面,通过不同的化学官能团,如甲基、氨基对金纳米粒子亲和性质的差异,实现了纳米粒子在固体表面的定点组装。     

金纳米粒子表面自组装巯基十一烷醇单分子层体系的制备及其光散射特性研究

采用柠檬酸钠还原法制备了水相金纳米粒子, 通过巯基的自组装, 成功获得了巯基十一烷醇(MUN)单分子层保护的金纳米粒子. 用紫外可见光谱、透射电子显微镜、激光散射粒度分析、同步散射光谱和发射光谱等手段对组装前后的金纳米粒子的性质进行了研究. 结果表明: 制备的金纳米粒子最大吸收波长518 nm, 形状规则, 粒度均匀, 平均粒径为14.6 nm, 每个粒子含有约9.64×10⁴原子; 组装之后的金纳米粒子表面等离子体共振吸收峰红移17.0 nm, 平均粒径增大为20.2 nm, 组装层的平均厚度2.8 nm, 与MUN分子长度相当, 结合量实验证明每一个金纳米粒子可以结合约7.52×10³个MUN, 表面覆盖率为83.6%, 粒子分散均匀, 稳定性增强可长期保存; 同步散射光谱变化和发射光谱中分频、差频和倍频峰的存在证明, 金纳米粒子组装前后均具有非线性光学特性.     

金纳米粒子-胱氨酸三维网状结构的形成及其光谱特性研究

用柠檬酸三钠还原法制备了水溶性金纳米粒子, 粒子的平均粒径为4.5 nm, 它与胱氨酸作用后, 胱氨酸利用双硫键在其表面成功地进行了自组装, 获得了金纳米粒子-胱氨酸的三维网状结构. 用紫外-可见光谱、光散射光谱、透射电子显微镜等手段对胱氨酸组装前后的金纳米粒子进行了表征. 结果显示, 粒子与粒子之间, 通过静电引力形成了离子键, 吸收光谱变化明显, 金纳米粒子特征吸收峰由组装前518 nm红移到670 nm, 溶液颜色也相应由酒红色变为蓝紫色, 求出了金纳米粒子-胱氨酸三维网状结构形成过程中胱氨酸的最佳量, 金与胱氨酸的物质的量比为1∶1. 对于4.5 nm的金纳米粒子, 只有14%左右的胱氨酸在金纳米粒子的表面进行了自组装, 而多余的86%的胱氨酸未与金纳米粒子作用; 其共振瑞利散射光谱具有潜在的应用价值. 该研究对以金纳米粒子为基础的新材料制备进行了有益的探索.     

Gold nanoparticles as a colorimetric sensor for protein conformational changes

Spherical gold nanoparticles and flat gold films are prepared in which yeast iso-1-cytochrome c (Cyt c) is covalently bound to the gold surface by a thiol group in the cystein 102 residue. Upon exposure to solutions of different pH, bound Cyt c unfolds at low pH and refolds at high pH. This conformational change causes measurable shifts in the color of the coated nanoparticle solutions detected by UV-VIS absorption spectroscopy and in the refractive index (RI) of the flat gold films detected by surface plasmon resonance (SPR) spectroscopy. Both experiments demonstrate the same trend with pH, suggesting the use of protein-covered gold nanoparticles as a simple colorimetric sensor for conformational change.     

Functionalized surface as template for in situ generation of two-dimensional metal nanoparticle assembly

Two-dimensional gold nanoparticle assemblies with an average nanoparticle size of 6 nm are generated on silicon and indium tin oxide (ITO)-coated glass surfaces, functionalized with polyethylenimine (PEI) silane monolayer. Contact angle measurements show increased hydrophilic character of the surface due to nanoparticle formation. X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) are used to monitor the chemical and structural development of these nanostructures, while UV–vis spectroscopy is used to follow the formation of the nanoparticle assemblies. This paper elucidates a simple route to in situ synthesis of surface immobilized gold nanoparticles under ambient conditions and also extends to the synthesis of other surface bound nanoparticles, like silver and platinum. Gold nanoparticle assemblies generated in this study are also catalytically active towards methanol oxidation reaction (MOR), which is relevant for direct methanol fuel cells (DMFCs).     

Dense aqueous colloidal gold nanoparticles prepared from highly concentrated precursor solution

Gold nanoparticles were fabricated by reduction of highly concentrated Au(III) ions (200 mM) with casein proteins from milk. The gold nanoparticles were converted to nanoparticle-powders after washing and subsequent vacuum drying without aggregation. The nanoparticle-powders completely re-dispersed in aqueous solution, and stable colloidal gold nanoparticles were obtained. UV-vis extinction spectra and dynamic light scattering (DLS) measurements revealed that large assemblies (size, ca. 3 μm) and subaggregates (size, <0.5 μm) composed of gold nanoparticle-casein protein chain-Au(III) ion were dynamically formed and disintegrated over the course of the growth of the gold nanoparticles. Fourier transform infrared (FT-IR) spectra indicated conformational changes of casein proteins induced by the interaction of casein protein-Au(III) ion and -gold nanoparticle. Finally, rapid, one-pot, and highly concentrated synthetic procedures of gold and silver nanoparticle powders protected by casein (mean diameters below 10 nm) were successfully developed using 3-amino-1-propanol aqueous solutions as reaction media. Dense colloidal gold (40 g L(-1)) and silver (22 g L(-1)) nanoparticle aqueous solutions were obtained by re-dispersing the metal nanoparticle powders.     

Controlling the self-assembly structure of magnetic nanoparticles and amphiphilic block-copolymers: from micelles to vesicles

We report how to control the self-assembly of magnetic nanoparticles and a prototypical amphiphilic block-copolymer composed of poly(acrylic acid) and polystyrene (PAA-b-PS). Three distinct structures were obtained by controlling the solvent-nanoparticle and polymer-nanoparticle interactions: (1) polymersomes densely packed with nanoparticles (magneto-polymersomes), (2) core-shell type polymer assemblies where nanoparticles are radially arranged at the interface between the polymer core and the shell (magneto-core shell), and (3) polymer micelles where nanoparticles are homogeneously incorporated (magneto-micelles). Importantly, we show that the incorporation of nanoparticles drastically affects the self-assembly structure of block-copolymers by modifying the relative volume ratio between the hydrophobic block and the hydrophilic block. As a consequence, the self-assembly of micelle-forming block-copolymers typically produces magneto-polymersomes instead of magneto-micelles. On the other hand, vesicle-forming polymers tend to form magneto-micelles due to the solubilization of nanoparticles in polymer assemblies. The nanoparticle-polymer interaction also controls the nanoparticle arrangement in the polymer matrix. In N,N-dimethylformamide (DMF) where PS is not well-solvated, nanoparticles segregate from PS and form unique radial assemblies. In tetrahydrofuran (THF), which is a good solvent for both nanoparticles and PS, nanoparticles are homogeneously distributed in the polymer matrix. Furthermore, we demonstrated that the morphology of nanoparticle-encapsulating polymer assemblies significantly affects their magnetic relaxation properties, emphasizing the importance of the self-assembly structure and nanoparticle arrangement as well as the size of the assemblies.     

Gold nanoparticles with perfluorothiolate ligands

Two syntheses of gold nanoparticles with fluorinated alkyl and aryl thiolate ligands are reported. The fluorous Au nanoparticles are smaller than previous gold fluor-capped examples, and are in the 44-75 Au atom size range. Fluoroalkyl thiolate-protected (1H,1H,2H,2H-perfluorodecanethiolate) nanoparticles synthesized by a Brust reaction are a mixture of (mainly) approximately 8.5 kDa (ca. 44 core atoms) and approximately 14 kDa (ca. 75 core atoms) species, by MALDI-mass spectrometry. This composition is consistent with thermogravimetric analysis (TGA) results of the ligand shell composition. 19F NMR spectra display a progressive line broadening of resonances for fluorine sites closer to the Au core. A second synthetic route used a (ligand replacement) reaction of pentafluorobenzenethiol with Au55(PPh3)12Cl6. The exchange is (as previously observed for nonfluorinated thiols) accompanied by nanoparticle core size changes to produce a polydisperse mixture within which a Au75 core species could be electrochemically discerned by its characteristic 0.74 V electrochemical energy gap. Further characterization of the polydisperse nanoparticle product was done by HPLC, TEM, TGA, optical spectroscopy, and NMR data. Both varieties of fluorous nanoparticles exhibit solubilities typical of perfluorinated materials, as opposed to proteo versions.     

Size-controlled synthesis of magnetite nanoparticles

Monodisperse magnetite nanoparticles have been synthesized by high-temperature solution-phase reaction of Fe(acac)3 in phenyl ether with alcohol, oleic acid, and oleylamine. Seed-mediated growth is used to control Fe3O4 nanoparticle size, and variously sized nanoparticles from 3 to 20 nm have been produced. The as-synthesized Fe3O4 nanoparticles have inverse spinel structure, and their assemblies can be transformed into gamma-Fe2O3 or alpha-Fe nanoparticle assemblies, depending on the annealing conditions. The reported procedure can be used as a general approach to various ferrite nanoparticles and nanoparticle superlattices.     

富精氨酸多肽修饰的金纳米粒子跨膜传输

考察了富精氨酸多肽功能化的金纳米粒子作为载体对细胞外物质的跨膜传输行为. 通过生物素(Biotin)与亲和素(Streptavidin)的亲和反应将具有特定跨膜功能的富精氨酸RRRRRRRR(R₈)多肽分子连接到多肽CALNN修饰的金纳米粒子表面, 实现粒子的功能化. 以荧光素为模型化合物, 利用激光共聚焦显微镜观察了纳米粒子的输送过程. 实验结果表明, 富精氨酸多肽功能化的金纳米粒子可以作为一种低毒高效的跨膜输送载体.     

Gold Nanoparticle Assemblies on Surfaces: Reactivity Tuning through Capping‐Layer and Cross‐Linker Design

The immobilization of metal nanoparticles (NPs) with molecular control over their organization is challenging. Herein, we report the formation of molecularly cross‐linked AuNP assemblies using a layer‐by‐layer approach. We observed four types of assemblies: 1) small aggregates of individual AuNPs, 2) large aggregates of individual AuNPs, 3) networks of fused AuNPs, and 4) gold islands. Interestingly, these assemblies with the different cross‐linkers and capping layers represent different stages in the complete fusion of AuNPs to afford islands of continuous gold. We demonstrate that the stability toward fusion of the nanoparticles of the on‐surface structures can be controlled by the reactivity of the cross‐linkers and the hydrophilicity/hydrophobicity of the nanoparticles.     

Production of Gold nanoparticles in aqueous solutions of cellulose derivatives

It is shown that gold nanoparticles can be produced using cellulose ethers, methylhydroxyethyl cellulose, and carboxymethyl cellulose as reducing agents that also play the role of nanoparticle stabilizers. Depending on the synthesis conditions, nanoparticle sizes vary in the range of 20–100 nm. The application of carboxymethyl cellulose as a stabilizer may give rise to the formation of a bimodal ensemble of nanoparticles with sizes of 4–5 and 30–40 nm. The differences in the mechanisms for the reduction and stabilization of gold nanoparticles in the presence of these cellulose derivatives are established by IR spectroscopy. The obtained colloidal dispersions of gold nanoparticles remain stable for a long time.     

In Situ Formation of Gold Nanoparticles within a Polymer Particle and Their Catalytic Activities in Various Chemical Reactions

Composite materials consisting of nanoscale gold particles and protective polymer shells were designed and tested as catalysts in various chemical reactions. Initially, the systematic incorporation of multiple gold nanoparticles into a poly(N-isopropylacrylamide) particle was achieved by an in situ method under light irradiation. The degree of gold nanoparticle loading, along with the structural and morphological properties, was examined as a function of the amount of initial gold ions and reducing agent. As these gold nanoparticles were physically-embedded within the polymer particle in the absence of strong interfacial interactions between the gold nanoparticles and polymer matrix, the readily-accessible surface of the gold nanoparticles with a highly increased stability allowed for their use as recyclable catalysts in oxidation, reduction, and coupling reactions. Overall, the ability to integrate catalytically-active metal nanoparticles within polymer particles in situ allows for designing novel composite materials for multi-purpose catalytic systems.     

Chemically Organizable Nanosized Materials Preparation and Applications

We are interested in fabricating well-organized assemblies of nanosized materials with wet chemical approaches for the purpose of investigating various interfacial and mesoscopic phenomena. The paper describes how to use self-assembling techniques to prepare assemblies of colloidal nanoparticles and single walled carbon nanotubes on solid surfaces. Gold nanocolloids are taken as the model system, including preparation of functionalized nanoparticles, assembling on tailored substrates, surface reorganization, and 1D, 0D controlled assembling with the aid of scanning probe lithography. The typical work we have been doing using these elaborated nanoparticle assemblies includes, the quantitative investigations of die electromagnetic coupling of particle-particle and particle-substrate in surface enhanced Raman scattering (SERS), the single electron tunneling in nanoparticle assemblies measured with scanning probe microscopy (SPM) technique, the atomic force microscopy (AFM) lithography using the surface-confined gold nanoparticles as mask.     

Bottom-up assembly of colloidal gold and silver nanostructures for designable plasmonic structures and metamaterials

We report on bottom-up assembly routes for fabricating plasmonic structures and metamaterials composed of colloidal gold and silver nanostructures, such as nanoparticles ("metatoms") and shape-controlled nanocrystals. Owing to their well-controlled sizes/shapes, facile surface functionalization, and excellent plasmonic properties in the visible and near-infrared regions, these nanoparticles and nanocrystals are excellent building blocks of plasmonic structures and metamaterials for optical applications. Recently, we have utilized two kinds of bottom-up techniques (i.e., multiple-probe-based nanomanipulation and layer-by-layer self-assembly) to fabricate strongly coupled plasmonic dimers, one-dimensional (1D) chains, and large-scale two-dimensional/three-dimensional (2D/3D) nanoparticle supercrystals. These coupled nanoparticle/nanocrystal assemblies exhibit unique and tunable plasmonic properties, depending on the material composition, size/shape, intergap distance, the number of composing nanoparticles/nanocrystals (1D chains), and the nanoparticle layer number in the case of 3D nanoparticle supercrystals. By studying these coupled nanoparticle/nanocrystal assemblies, the fundamental plasmonic metamaterial effects could be investigated in detail under well-prepared and previously unexplored experimental settings.     

Gold nanoparticle self-assembly in two-component lipid Langmuir monolayers

Self-assembly processes are considered to be fundamental factors in supramolecular chemistry. Langmuir monolayers of surfactants or lipids have been shown to constitute effective 2D "templates" for self-assembled nanoparticles and colloids. Here we show that alkyl-coated gold nanoparticles (Au NPs) adopt distinct configurations when incorporated within Langmuir monolayers comprising two lipid components at different mole ratios. Thermodynamic and microscopy analyses reveal that the organization of the Au NP aggregates is governed by both lipid components. In particular, we show that the configurations of the NP assemblies were significantly affected by the extent of molecular interactions between the two lipid components within the monolayer and the monolayer phases formed by each individual lipid. This study demonstrates that multicomponent Langmuir monolayers significantly modulate the self-assembly properties of embedded Au NPs and that parameters such as the monolayer composition, surface pressure, and temperature significantly affect the 2D nanoparticle organization.     

Gold glyconanoparticles for mimics and measurement of metal ion-mediated carbohydrate-carbohydrate interactions

To mimic and measure calcium ion-mediated carbohydrate-carbohydrate interactions, four lactose derivatives have been synthesized for assembly on gold nanoparticles. The series of lactose derivatives varied by the length of the thiolated ethylene glycol anchor chain [O(CH2CH2O)(m)CH2CH2SH; where m = 0, 1, 2, and 3] used to self-assemble the carbohydrates to the preformed gold nanoparticles of ca. 16 nm diameter. Upon addition of calcium ions to the lactose-stabilized nanoparticles, rapid carbohydrate-carbohydrate interactions were visualized and subsequently measured using UV-visible spectrometry and transmission electron microscopy (TEM). The nanoparticle aggregates formed via metal-mediated carbohydrate-carbohydrate interactions could be readily redispersed through the addition of EDTA. Multiple reaggregation and redispersion cycles were achieved, confirming that the aggregation process was due to metal ion-mediated carbohydrate interactions rather than calcium chelation by residual citrate ions on the particle surface. The essential involvement of the lactose moiety in Ca2+ complexation was shown by control measurements on related D-glucose-derivatized nanoparticles, where a significantly reduced aggregation response was obtained only at high ion concentrations. Other group 2 metal ions with radii larger than that of calcium, viz., barium and strontium, were also shown to mediate the aggregation of the lactose-stabilized nanoparticles. The induced aggregation of the lactose nanoparticles was determined to be quantitatively dependent upon the calcium ion concentration. Furthermore, the analytical sensitivity of the calcium-induced aggregation and the linear dynamic range were dependent on the length of the ethylene glycol anchor chain. The shortest ethylene glycol chain (m = 0) gave the most sensitive response with the optimum limit of detection (0.8 mM Ca2+), whereas the longest ethylene glycol chain (m = 3) provides a measurement of calcium ion concentration over the largest linear dynamic range (10-35 mM Ca2+). This work has shown that the self-assembled deposition of lactose derivatives on gold nanoparticles provides multivalent carbohydrate surfaces that can be used as mimics for the measurement of biologically relevant carbohydrate-carbohydrate interactions. Additionally, this study has highlighted the importance of the structure and length of the ligand that anchors the carbohydrate sugar to the gold particle surface to facilitate such carbohydrate interactions and for "tuning" the analytical characteristics of bioassays developed using metal nanoparticle technology.     

Detection of Vibrational Spectroscopic Biomarkers of the Effect of Gold Nanoparticles on Wheat Seedlings Using Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy

The aim of this study is to evaluate the biochemical changes in the leaves of wheat seedlings exposed to gold nanoparticles (AuNPs) nondestructively and rapidly using attenuated total reflectance Fourier transform infrared spectroscopy and laser-induced fluorescence. The 18?nm size gold nanoparticles are synthesized by citrate reduction. For analyzing the effect of gold nanoparticles on wheat seedlings, the treatment of gold nanoparticles was applied to the seedlings through roots and following the spectroscopic measurement of biochemical signatures. The laser-induced fluorescence measurement has been performed to access the effect of gold nanoparticles on the chlorophyll concentration of wheat seedlings. The decrease in the fluorescence intensity and the fluorescence intensity ratio on the treatment of gold nanoparticles indicates increase in the concentration of chlorophyll in the leaves of wheat seedlings. The attenuated total reflectance Fourier transform infrarred spectroscopy in combination with principal component analysis has been used to visualize the biochemical changes in the cellulose, hemicellulose, pectin, lignin, amino acids, proteins, and lipid of the leaves of wheat seedlings by recording infrared spectra in the region from 4000 to 400?cm^?1. Principal component analysis applied to the preprocessed infrared data clearly distinguishes the spectral variability between control and gold nanoparticle treated seedlings. The study shows that exposure of gold nanoparticles increases the concentrations of cellulose, hemicelluloses, pectin, and lignin in the leaves of wheat seedlings. The increase in these chemicals indicates the modulation of cell walls of the wheat seedlings by the gold nanoparticle treatment. The exposure to gold nanoparticles also enhances the expression of lipid and proteins in the leaves of wheat seedlings.