高定向石墨表面金纳米粒子和金纳米线的研究

利用真空沉积方法在高定向石墨(HOPG)基底上直接制备了粒径分布较小的金纳米粒子.超高真空扫描隧道显微镜(STM)研究发现,在74℃退火后,表观直径为2.5?nm的金纳米粒子在HOPG基底上形成了排列均匀的准一维纳米粒子链,并且此金纳米粒子链结构稳定.在122℃退火后,不同粒径的金纳米粒子在HOPG基底表面上聚合长大形成了准一维金纳米线.这一发现为制备由金粒子组成的有序纳米结构开辟了探索途径.     

高定向石墨表面金纳米粒子和金纳米线的研究

利用真空沉积方法在高定向石墨(HOPG)基底上直接制备了粒径分布较小的金纳米粒子.超高真空扫描隧道显微镜(STM)研究发现,在74℃退火后,表观直径为2.5nm的金纳米粒子在HOPG基底上形成了排列均匀的准一维纳米粒子链,并且此金纳米粒子链结构稳定.在122℃退火后,不同粒径的金纳米粒子在HOPG基底表面上聚合长大形成了准一维金纳米线.这一发现为制备由金粒子组成的有序纳米结构开辟了探索途径.     

不同粒径、超均匀球形金纳米粒子合成及其表面增强拉曼散射效应研究

以氯金酸为原料,抗坏血酸为还原剂,柠檬酸钠为保护剂,用化学还原(种子生长)法制备了不同粒径、超均匀的球形金纳米粒子溶胶,并通过紫外可见吸收光谱(UV-Vis)和扫描电子显微镜(SEM)进行表征。结果表明,随着金纳米粒子粒径的增大,其UV-Vis光谱中的吸收峰发生红移并出现四极峰。为进一步研究金纳米粒子表面增强拉曼散射(SERS)效应的作用机理并优化其灵敏度,我们以罗丹明6G(R6G)为探针分子,对不同粒径的金纳米粒子进行SERS表征,发现R6G的SERS信号随着金纳米粒子的增大先增强后减弱。当金纳米粒子的平均粒径达到120 nm时,产生最强SERS信号增强,增强因子约为1.1×107。三维时域有限差分法(3D-FDTD)理论模拟纳米粒子阵列电磁场分布结果与实验数据的趋势一致。     

一种制备金纳米粒子的新方法

报道了一种温和的、低成本、有效制备高纯度单分散金纳米粒子的新方法.采用种子生长法,在表面活性剂十八烷基苄基二甲基氯化铵(BDAC)体系下液相合成金纳米粒子.通过改变实验中反应温度和反应时间等条件,制备了粒径为25-50nm的金纳米粒子,运用透射电子显微镜(TEM)对纳米粒子的形貌进行分析,利用紫外可见光谱(UV-Vis)对产物进行光谱表征,并讨论了金纳米粒子的形成机制.结果表明,金纳米粒子的粒径随反应温度的升高及反应时间的加长有增大的趋势.     

金银纳米粒子的电化学性质及联苯胺的SERS研究

采用柠檬酸钠还原氯金酸,硼氢化钠还原硝酸银分别制备了较小粒径的金、银纳米粒子。运用紫外可见吸收光谱(UV-Vis)、扫描电子显微镜(SEM)、循环伏安法(CV)对金、银纳米粒子进行了表征。结果表明：所得金、银纳米粒子粒径分别约为16和10 nm,并能以亚单层形式组装于导电玻璃(ITO)表面;CV图显示金、银纳米粒子分别有一对不对称的氧化还原峰,而且纳米粒子的浓度对其氧化还原电位存在一定的影响。采用自组装方法,以联苯胺为偶联分子, 在粗糙金基底表面构筑了金/银纳米粒子的双层有序结构。表面增强拉曼光谱研究表明, 在有序金银纳米粒子组装体中偶联分子的拉曼散射得到了增强。     

不同形貌金纳米粒子的制备及其表面增强拉曼散射效应的研究

不同形状的金纳米粒子在表面增强拉曼散射(surface enhanced Raman scattering,SERS)中有不同的增强效果,多面体金纳米粒子具有多角结构,显示出比金纳米板更为明显的增强效果,近年来对其合成和性质的研究备受关注。该研究探究了十二面体,二十面体,三角板,球形四种形状的金纳米粒子在SERS中不同的增强效果。分别采用硼氢化钠还原法和以N,N-二甲基甲酰胺(DMF)为还原剂制备金三角纳米片和二十面体金纳米粒子,又以二十面体金纳米粒子为种子制备出十二面体金纳米粒子,并分别以以上三种不同形貌的金纳米粒子及球形金溶胶为基底,4-巯基吡啶,对巯基苯甲酸为探针分子检测了其在不同激发波长下的增强效果。透射电子显微镜结果表明金三角纳米板的平均边长为130nm,二十面体和十二面体金纳米粒子的粒径分别为100和120nm。三者的紫外可见吸收峰分别在589,598和544nm处。表面增强拉曼散射结果表明金多面体比金三角纳米板表现出更好的增强效果。     

三维时域有限差分法计算金纳米粒子尺寸与SERS活性的关联

通过合成一系列不同粒径(16～160 nm)的金纳米粒子.观察到120～135 nm的金纳米粒子在632.8nm波长激发下具有最高的SERS活性,这与前人报道的电磁场理论及实验的结果不同.利用三维时域有限差分法对金纳米粒子的SERS活性与其尺寸以及入射光波长的关系进行模拟计算.在632.8 nm激发线下,金纳米粒子二聚体体系在粒径为110 nm左右具有最佳增强效应,其光电场耦合最强的热点处的增强因子高达109考虑到体系的平均SERS增强因子通常会比最大值低约2个数量级,计算得到的107的增强因子与实验测量值相符.同时对目前实验上尚难以合成的大尺寸的金纳米粒子进行模拟,结果表明受多极矩和大尺寸效应的影响在粒径220 nm时又出现SERS增强另一峰值.在325 nm的紫外激发线下,计算得到的增强因子仅为102.     

不同表面结构的金纳米粒子荧光性质.

"研究了具有不同表面结构的金纳米粒子：裸金纳米粒子、三苯基膦修饰的金纳米粒子、巯基丙酸表面取代的金纳米粒子的荧光性质,及其对CdSe纳米粒子的荧光猝灭作用．发现不同的金纳米粒子荧光信号受粒子表面一价金离子与配体分子之间相互作用的影响,其荧光强度对其表面分子具有强烈的敏感性;具有不同表面结构的金纳米粒子对CdSe纳米粒子的荧光猝灭作用不同,与其吸收光谱和CdSe纳米粒子发射光谱的重叠程度相关."     

不同粒径金纳米微粒对荧光素钠的猝灭效应研究

采用柠檬酸盐合成法制备了不同粒径的金纳米微粒,用吸收光谱和透射电镜对金纳米微粒进行了表征。研究了不同粒径金纳米微粒与荧光素钠分子的相互作用。发现金纳米微粒对荧光素钠具有荧光猝灭效应, 并且其荧光猝灭程度与金纳米微粒的粒径大小有关。随着金纳米微粒粒径的减小,荧光猝灭程度增大。探讨了金纳米微粒对荧光素钠荧光猝灭的机理,表明该荧光猝灭为动态猝灭。     

金纳米粒子自组装薄膜的光谱学研究

采用柠檬酸钠还原氯金酸制备了金胶体，通过静电自组装制备了金纳米粒子薄膜，利用紫外-可见光吸收光谱等对金纳米粒子薄膜进行了光谱学研究，紫外-可见光吸收光谱表明所制备的金溶胶为单分散体系，根据自组装薄膜的X-射线衍射谱，由谢乐公式估算金纳米粒子的粒径约为21nm；X-射线光电子能谱显示氯金酸的还原反应比较完全，金主要以Au^0的价态存在，金胶体粒子通过静电吸引机制组装到PDDA改性的衬底表面；紫外-可见光吸收光谱和表面增强拉曼光谱显示，由于粒子间的电磁耦合，自组装金纳米粒子薄膜表现出协同等离子体共振吸收行为和表面增强拉曼散射效应。     

Au/Al2O3催化剂的UV-Vis谱研究

研究了十六烷基三甲基溴化铵 (CTAB) /正己醇 /水体系的W/O微乳体系中 ,几种主要实验参数对用NaBH4还原氯金酸溶液制得的金纳米粒子大小的影响。实验结果表明 :微乳体系中水与表面活性剂的摩尔比rw 在所研究的范围内对金粒子大小影响不大 ,而氯金酸溶液的浓度对金粒子大小影响较大。通过优化制备条件 ,用两种不同的方法制备了Au/Al2 O3 催化剂 ,并用紫外 可见光谱、透射电镜 (TEM)和X射线衍射(XRD)对其进行表征 ,初步考察了不同制备方法对催化剂中活性组分Au粒大小的影响     

Gold‐Nanoparticle‐Assisted Self‐Assembly of Chemical Gradients with Tunable Sub‐50 nm Molecular Domains

A simple and efficient principle for nanopatterning with wide applicability in the sub‐50 nanometer regime is chemisorption of nanoparticles; at homogeneous substrates, particles carrying surface charge may spontaneously self‐organize due to the electrostatic repulsion between adjacent particles. Guided by this principle, a method is presented to design, self‐assemble, and chemically functionalize gradient nanopatterns where the size of molecular domains can be tuned to match the level corresponding to single protein binding events. To modulate the binding of negatively charged gold nanoparticles both locally (<100 nm) and globally (>100 μm) onto a single modified gold substrate, ion diffusion is used to achieve spatial control of the particles’ mutual electrostatic interactions. By subsequent tailoring of different molecules to surface‐immobilized particles and the void areas surrounding them, nanopatterns are obtained with variable chemical domains along the gradient surface. Fimbriated Escherichia coli bacteria are bound to gradient nanopatterns with similar molecular composition and macroscopic contact angle, but different sizes of nanoscopic presentation of adhesive (hydrophobic) and repellent poly(ethylene) glycol (PEG) domains. It is shown that small hydrophobic domains, similar in size to the diameter of the bacterial fimbriae, supported firmly attached bacteria resembling catch‐bond binding, whereas a high number of loosely adhered bacteria are observed on larger hydrophobic domains.     

Gold nanoparticles produced by laser ablation in water and in graphene oxide suspension

The comparison between two different approaches based on the use of the laser ablation in medium to synthetise gold nanoparticles is presented and discussed. Deionised water as well as a graphene oxide (GO) suspension in deionised water have been employed as solution to produce gold nanoparticles by laser ablation. In the former case, the nanoparticles assembly has been stabilised by using surfactants, but in the latter case to avoid undesired effects the use of chemicals was not necessary and Au reduced graphene oxide (Au-rGO) nanocomposites have been obtained. The structure, size and composition of the gold nanoparticles and of the Au–rGO nanocomposites have been monitored by UV–Vis–NIR absorption spectroscopy and Raman spectroscopy, the transmission and scanning electron microscopies and the X-ray energy-dispersive spectroscopy. The presented methodology of Au rGO nanocomposites preparation could represent a green alternative on the production of metallic nanoparticles in biocompatible environment.     

Targeted and Specific Modification with 4-Carboxybenzeneboronic Acid and TPGS of Fluorescent Gold Nanoparticles and the Enhanced Antitumor Activity Research

A targeting and specific fluorescent gold nanoparticle is prepared for tracing of drug and effective treatment of cancers. First, 4-carboxybenzeneboronic acid (CBPA) and D-α-tocopheryl polyethylene glycol 1000 succinate (TPGS) are used to modify cyclodextrins (CDs), then modified cyclodextrins and polyethylene glycol (PEG) are used to stabilize gold nanoclusters to prepare fluorescent gold nanoparticles (AuNCs@CD-TPGS-CBPA/PEG). CBPA has targeting and TPGS can induce apoptosis, therefore, AuNCs@CD-TPGS-CBPA/PEG has targeting and certain anti-tumor activity. The structure and morphology of the nanomaterial are characterized by using nuclear magnetic resonance (NMR) spectroscopy and transmission electron microscope (TEM). Paclitaxel (PTX) is loaded into the hydrophobic cavity of CDs to form targeting specific drug-loaded fluorescent gold nanoparticles (AuNCs@CD-TPGS-CBPA/PEG/PTX). Biological performances of AuNCs@CD-TPGS-CBPA/PEG are studied by in vitro and in vivo experiments. In vitro test results confirm that AuNCs@CD-TPGS-CBPA/PEG could be internalized by tumor cells, and effectively against tumor cells, but it is biocompatible to normal cells. In vivo experiments prove that AuNCs@CD-TPGS-CBPA/PEG has excellent targeting, biocompatibility, and enhanced antitumor capability, could enrich and stay for a long time in the tumor regions, effectively prolong the lifetime of tumor-bearing mice. Therefore, this work provides an insight into the development of fluorescent gold nanomaterials for practical biomedical application.     

Development of a Liver‐Targeting Gold–PEG–Galactose Nanoparticle Platform and a Structure–Function Study

For the specific liver parenchymal cell delivery, a series of short heterobifunctional poly(ethylene glycol) (PEG) derivatives containing dimercapto and galactose (Gal) terminals is synthesized for the preparation of gold conjugates. The Gal density on the surface of all gold conjugates can be well controlled and the prepared gold conjugates are stable in various media, even in the presence of serum. For the liver targeting and reflectance imaging applications, the structure–function relationships of this platform, including the influence of the PEG molecular weight and the Gal ligand coverage of hybrid particles on the cytotoxicity and cellular recognition of tumor cells in vitro and on their liver‐targeting ability in small animals, are studied. Biocompatibility results show that HepG2 cells are more sensitive than HeLa cells to gold conjugates. Cellular uptake studies demonstrate that a lower PEG molecular weight, a higher Gal density, or a higher gold concentration can increase the cellular uptake efficiency of these hybrid particles in HepG2 cells when the other parameters are constant. The results reveal the importance of parameter modulation for the design and control of nanoprobes and the gold conjugates with short PEG chains and a high Gal density are a potential vector for active‐targeting therapy.     

Control of Surface Ligand Density on PEGylated Gold Nanoparticles for Optimized Cancer Cell Uptake

Surface chemistry plays a critical role in the solution phase behavior of gold nanoparticles (Au NPs) for applications such as in situ diagnostics and drug delivery. Polyethylene glycol (PEG), a hydrophilic polymer with low immunogenicity, is most commonly used for protecting Au NPs for biomedical applications. The ligand density and molecular weight of PEG on the gold nanoparticle surface are key factors that control the particles’ behavior. Specifically, the total density of PEG ligands gives rise to a transition from a disorganized, deformable polymer “mushroom” orientation to a more rigid “brush” orientation. Here, it is investigated how to rationally control this transition for Au NPs coated with PEG‐SH molecules within the weight range of 0.55 to 5 kDa, and evaluate their subsequent interaction with cancer cells. Several complementary methods are used to evaluate the effect of PEGylation on biologically relevant aspects, including surface ligand density, hydrodynamic size, dispersity, and cellular toxicity. In this work, the optimal synthesis ratios of PEG:Au NPs for achieving stability and maximum dispersity with 0.55, 1, 2, and 5 kDa PEG are determined to be 2500, 700, 500, and 300, respectively. Importantly, ratios that exceed those necessary for maximum dispersion of the Au NPs as determined by UV–vis and DLS are found to be the best ratios for highest cell viability.     

One-pot synthesis of gold/poly(3,4-ethylendioxythiophene) nanocomposite

In this paper, we report the preparation of highly stable gold nanoparticles/poly(3,4-ethylendioxythiophene) nanocomposites by a one-pot chemical route in aqueous medium without surfactants to increase the solubility of the monomer (3,4-ethylendioxythiophene, EDOT) or to stabilize gold nanoparticles (Au NPs). The generation of the nanocomposite was followed by UV–Visible transmission spectroscopy combined with multivariate curve resolution alternating least squares analysis to deconvolute the individual spectra of the different species generated in the synthesis: oligomers, polymer and gold nanoparticles. The plasmon band observed at 530 nm during the synthesis step indicates the generation of gold nanoparticles. The influence of monomer and metal precursor concentration and their concentration ratios on Au NP size were analyzed. The electrochromic properties of the composite were investigated by UV–Visible absorption spectroelectrochemistry, being mainly related to polymer oxidation and reduction. The main difference observed is the hypsochromic shift of the polymer spectra due to the gold nanoparticles inside the polymer. Multicyclic spectroelectrochemical experiments evidence a high stability and adhesion of the nanocomposite.     

Study of tryptophan assisted synthesis of gold nanoparticles by combining UV–Vis, fluorescence, and SERS spectroscopy

We developed a rapid and non-toxic method for the preparation of colloidal gold nanoparticles (GNPs) by using tryptophan (Trp) as reducing/stabilizing agent. We show that the temperature has a major influence on the kinetics of gold ion reduction and the crystal growth, higher temperatures favoring the synthesis of anisotropic nanoparticles (triangles and hexagons). The as-synthesized nanostructures were characterized by UV–Vis absorption spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), fluorescence, and surface-enhanced Raman scattering (SERS) spectroscopy. The UV–Vis measurements confirmed that temperature is a critical factor in the synthesis process, having a major effect on the shape of the synthesized GNPs. Moreover, fluorescence spectroscopy was able to monitor the quenching of the Trp fluorescence during the in situ synthesis of GNPs. Using Trp as molecular analyte to evaluate the SERS efficiency of as-prepared GNPs at different temperatures, we demonstrated that the Raman enhancement of the synthesized gold nanoplates is higher than that of the gold spherical nanoparticles.     

碳纳米管表面金纳米颗粒的形成与结构转变

利用分子动力学模拟研究了室温下金纳米颗粒在碳纳米管表面的结构和作用能.研究结果表明,金纳米颗粒随着尺寸的增大会发生不同于孤立状态下的结构转变.当原子数小于130时,颗粒属于无序结构;当原子数大于140时,呈现面心立方晶体结构.小金纳米颗粒和碳纳米管结合紧密,相互作用能正比于面对碳纳米管的颗粒表面面积. 关键词： 金纳米颗粒 碳纳米管 分子动力学模拟     

Structure and Stability of PEG‐ and Mixed PEG‐Layer‐Coated Nanoparticles at High Particle Concentrations Studied In Situ by Small‐Angle X‐Ray Scattering

Ligand‐layer structure and stability of gold nanoparticles (AuNP) coated with α‐methoxypoly(ethylene glycol)‐ω‐(11‐mercaptoundecanoate) (PEGMUA) layers and mixed layers of PEGMUA and 11‐mercaptoundecanoic acid (MUA) at high AuNP concentrations are studied in situ by small‐angle X‐ray scattering (SAXS). The thickness of the ligand layer is modified by the molecular weight of the PEG‐ligands (2 and 5 kDa), and the PEG‐grafting density is decreased by coadsorption of MUA. The response of the conjugates to a pressure of up to 4 kbar is probed. The results indicate strongly hydrated PEG layers at high grafting densities. The stability of the mixed ligand‐layer conjugates is lower. This is most probably due to enhanced interparticle PEG–PEG interactions at lower grafting densities. The presented study demonstrates that a detailed structural characterization of polymer ligand layers in situ and in response to external stimuli is possible with SAXS.