Characterization of Ag/Pt core-shell nanoparticles by UV-vis absorption, resonance light-scattering techniques

The water-soluble Ag/Pt core-shell nanoparticles were prepared by deposition Pt over Ag colloidal seeds with the seed-growth method using K2PtCl4 with trisodium citrate as reduced agent. The Ag:Pt ratio is varied from 9:1 to 1:3 for synthesizing Pt shell layer of different thickness. A remarkable shift and broadening of Ag surface plasmon band around 410 nm was observed. The contrast of TEM images of Ag/Pt colloids has been obtained. Various techniques, such as transmission electron microscopy (TEM), UV-vis absorption and resonance light-scattering spectroscopy were used to characterize nanoparticles. The data of TEM, UV-vis and resonance light-scattering spectrum all confirm formation of Ag/Pt core-shell nanoparticles. Resonance light-scattering and emission spectrum show the Ag and Ag/Pt core-shell nanoparticles have a nonlinear light-scattering characteristic.     

Synthesis and plasmonic properties of silver and gold nanoshells on polystyrene cores of different size and of gold–silver core–shell nanostructures

Simple methods of preparing silver and gold nanoshells on the surfaces of monodispersed polystyrene microspheres of different sizes as well as of silver nanoshells on free-standing gold nanoparticles are presented. The plasmon resonance absorption spectra of these materials are presented and compared to predictions of extended Mie scattering theory. Both silver and gold nanoshells were grown on polystyrene microspheres with diameters ranging from 188 to 543 nm. The commercially available, initially carboxylate-terminated polystyrene spheres were reacted with 2-aminoethanethiol hydrochloride (AET) to yield thiol-terminated microspheres to which gold nanoparticles were then attached. Reduction of silver nitrate or gold hydroxide onto these gold-decorated microspheres resulted in increasing coverage of silver or gold on the polystyrene core. The nanoshells were characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM) and UV–vis spectroscopy. By varying the core size of the polystyrene particles and the amount of metal (silver or gold) reduced onto them, the surface plasmon resonance of the nanoshell could be tuned across the visible and the near-infrared regions of the electromagnetic spectrum. Necklace-like chain aggregate structures of gold core–silver shell nanoparticles were formed by reducing silver nitrate onto free citrate-gold nanoparticles. The plasmon resonance absorption of these nanoparticles could also be systematically tuned across the visible spectrum.     

Two-dimensional self-organization of polystyrene-capped gold nanoparticles

Thiol end-functionalized polystyrene chains have been introduced onto the surface of gold nanoparticles via a two-step grafting-to method. This simple grafting procedure is demonstrated to be efficient for gold nanoparticles of different sizes and for particles initially dispersed in either aqueous or organic media. The method has been applied successfully for a relatively large range of polystyrene chain lengths. Grafting densities, as determined by thermogravimetric analysis, are found to decrease with increasing chain length. In all cases, the grafting density indicates a dense brush conformation for the tethered chains. The resulting functionalized nanoparticles self-organize into hexagonally ordered monolayers when cast onto solid substrates from chloroform solution. Furthermore, the distance between the gold cores in the dried monolayer is controlled by the molecular weight of the grafted polystyrene. Optical absorption spectra recorded for the organized monolayers show the characteristic plasmon absorption of the gold particles. Importantly, the plasmon resonance frequency exhibits a distinct dependence on interparticle separation that can be attributed to plasmon coupling between neighboring gold cores.     

Morphologies and surface plasmon resonance properties of monodisperse bumpy gold nanoparticles

The influence of the morphology of gold nanoparticles on the surface plasmon resonance was investigated experimentally and theoretically. Highly monodisperse bumpy gold nanoparticles of increasing size were synthesized, and the surface plasmon resonance wavelength shifted to longer wavelengths more rapidly with increasing particle size for bumpy particles than for spherical gold nanoparticles. The detailed surface morphology of bumpy gold nanoparticles was characterized by AFM, TEM, and SEM, and the optical properties were investigated on a single particle level. The comparison of the plasmon resonant properties between bumpy and spherical gold nanoparticles was also examined with a theoretical model.     

High-density assembly of gold nanoparticles on multiwalled carbon nanotubes using 1-pyrenemethylamine as interlinker

In this article, we describe the formation of carbon nanotube (CNT)-gold nanoparticle composites in aqueous solution using 1-pyrenemethylamine (Py-CH2NH2) as the interlinker. The alkylamine substituent of 1-pyrenemethylamine binds to a gold nanoparticle, while the pyrene chromophore is noncovalently attached to the sidewall of a carbon nanotube via pi-pi stacking interaction. Using this strategy, gold nanoparticles with diameters of 2-4 nm can be densely assembled on the sidewalls of multiwalled carbon nanotubes. The formation of functionalized gold nanoparticles and CNT-Au nanoparticle composites was followed by UV-vis absorption and luminescence spectroscopy. After functionalization of gold nanoparticles with 1-pyrenemethylamine, the distinct absorption vibronic structure of the pyrene chromophore was greatly perturbed and its absorbance value was decreased. There was also a corresponding red shift of the surface plasmon resonance (SPR) absorption band of the gold nanoparticles after surface modification from 508 to 556 nm due to interparticle plasmon coupling. Further reduction of the pyrene chromophore absorbance was observed upon formation of the CNT-Au nanoparticle composites. The photoluminescence of 1-pyrenemethylamine was largely quenched after attaching to gold nanoparticles; formation of the CNT-Au nanoparticle composites further lowered its emission intensity. The pyrene fluoroprobe also sensed a relatively nonpolar environment after its attachment to the nanotube surface. The present approach to forming high-density deposition of gold nanoparticles on the surface of multiwalled carbon nanotubes can be extended to other molecules with similar structures such as N-(1-naphthyl)ethylenediamine and phenethylamine, demonstrating the generality of this strategy for making CNT-Au nanostructure composites.     

Supramolecular layer-by-layer assembly: alternating adsorptions of guest- and host-functionalized molecules and particles using multivalent supramolecular interactions

The stepwise construction of a novel kind of self-assembled organic/inorganic multilayers based on multivalent supramolecular interactions between guest-functionalized dendrimers and host-modified gold nanoparticles has been developed, yielding supramolecular layer-by-layer assembly. The deposition process was monitored by surface plasmon resonance spectroscopy. Further characterization of the multilayer films was performed by means of UV/vis absorption spectroscopy, which showed a linear increase in absorption with the number of bilayers. The growth of the gold nanoparticle plasmon absorption band corresponded to approximately a dense monolayer of gold nanoparticles per bilayer. Ellipsometry and atomic force microscopy (AFM) scratching experiments were used to measure the development of the film thickness with the number of bilayers, confirming linear growth and a thickness increase of approximately 2 nm/bilayer.     

Reversible Modulation of Surface Plasmons in Gold Nanoparticles Enabled by Surface Redox Chemistry

Switchable surface redox chemistry is demonstrated in gold@iron/iron oxide core–shell nanoparticles with ambient oxidation and plasmon‐mediated reduction to modulate the oxidation state of shell layers. The iron shell can be oxidized to iron oxide through ambient oxidation, leading to an enhancement and red‐shift of the gold surface plasmon resonance (SPR). This enhanced gold SPR can drive reduction of the iron oxide shell under broadband illumination to reversibly blue‐shift and significantly dampen gold SPR absorption. The observed phenomena provide a unique mechanism for controlling the plasmonic properties and surface chemistry of small metal nanoparticles.     

Electrochemical formation of crooked gold nanorods and gold networked structures by the additive organic solvent

Crooked gold nanorods (CGNRs) and gold network structures are fabricated using a simple electrochemical approach. The growth solution is prepared by surfactant solution as micelle templates with isopropanol (IPA) solvent. The shape of crooked nanorods and networks structure depend on the amount of added IPA solvent. To investigate the influence of isopropanol solvent on the CGNRs, the amount of IPA was varied in the range from 0.05 to 0.2 mL. It was found that the aspect ratios (gamma) of CGNRs were in the range from 1.06 to 1.46, and the UV-vis absorption measurement revealed a pronounced red-shift of the surface plasmon resonance (SPR) band from 532 to 560 nm. High-resolution transmission electron microscopy (HRTEM) showed that the formation of crooked nanorod structure was induced by aggregation of many small gold nuclei between the several large gold nanoparticles during growth, causing the small gold nuclei to link the gold nanoparticles. The CGNRs have a polycrystalline structure via the analysis from selected-area electron diffraction (SAED).     

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.     

Dipole-dipole plasmon interactions in gold-on-polystyrene composites

Red-shifting of the optical absorption spectra of aggregates of gold nanoparticles by dipole-dipole interactions is of considerable interest, both for theoretical reasons and because the phenomenon can be potentially exploited in various applications. A convenient and practical way to control the effect is to assemble the aggregated ensemble of n gold nanoparticles on the outer surface of larger dielectric spheres. Here, we show by experiment and calculation how the spectra of these structures can be systematically morphed from that of isolated gold particles, through the regime of broad absorption dominated by particle-particle interactions, and finally to the limiting case of a continuous nanoshell. The experimental data were produced using the process of deposition-precipitation, which provides a facile method to decorate polystyrene microspheres with gold nanoparticles. There is no need for prior functionalization of the microsphere surface in our method of deposition-precipitation. Calculations were carried out using a code based on the discrete dipole approximation (DDA). The spectra were dominated by three effects. These were a peak absorption at about 540 nm produced by the conventional plasmon resonance of spherical gold nanoparticles, a broad absorption in the range 600-900 nm caused by diverse dipole-dipole interactions between particles, which strengthened as the number of attached gold particles increased and finally, when n was large, an absorption peak due to the onset of nanoshell-like resonances. The experimental spectra could be successfully fitted by spectra calculated using combinations of these effects.     

Effect of the structure of a network matrix on the formation of gold nanoparticles during photoreduction of its salts in solutions of acrylic oligomers

The effect of network parameters of three-dimensionally crosslinked polyacrylic optically transparent matrices on the generation of surface plasmon resonance of gold nanoparticles forming during irradiation of Au³⁺ salt solutions in a liquid acrylic composite is studied. During the UV irradiation of a solution, the photoreduction of gold and the photoinitiated polymerization of acrylates proceed simultaneously to form transparent colorless films in which, after subsequent light and/or heat treatment, an absorption band near 550 nm that corresponds to the plasmon resonance of nanosize metal particles is generated. During the photoreduction of gold salt in matrices of oligo(urethane acrylate) composites with similar structures of the oligomeric block, the parameters of the three-dimensional network—the internodal and interchain distances—affect the rate of generation of gold nanoparticles but not the limiting value of optical density for the plasmon-resonance band of nanoparticles. Polyacrylate matrices may serve as a registering medium for optical data recording.     

Preparation of biotinylated glyconanoparticles via a photochemical process and study of their bioconjugation to streptavidin

We report here the preparation of novel biotinylated glyconanoparticles from well-defined biotinylated glycopolymers and poly(N-isopropylacrylamide) (PNIPAAm) synthesized via the reversible addition fragmentation chain transfer (RAFT) polymerization process. The in situ reduction of the biotinylated glycopolymers, PNIPAAm, poly(ethylene glycol), and HAuCl4 via a photochemical process resulted in the formation of biotinylated gold nanoparticles. The multifunctional biotinylated glyconanoparticles were then evaluated for their bioconjugation toward streptavidin using UV-vis spectroscopy and surface plasmon resonance (SPR). The biotinylated nanoparticles underwent aggregation in the presence of streptavidin as revealed by spectrophotometry, which indicates the accessibility of the biotin for conjugation. These results were further confirmed by surface plasmon resonance even in the case of surface-immobilized streptavidin.     

以金纳米粒子为探针比色法检测顺铂

报道了一种以金纳米粒子表面等离子吸收带变化为基础, 通过DNA与cis-Pt相互作用来检测溶液中cis-Pt浓度的新型比色法.     

Construction of simple gold nanoparticle aggregates with controlled plasmon–plasmon interactions

We have developed a colloidal assembly for the study of plasmon–plasmon interactions between gold nanoparticles. Colloidal aggregates of controlled size and interparticle spacing were synthesized on silica nanoparticle substrates. Following the immobilization of isolated gold nanoparticles onto silica nanoparticles, the surfaces of the adsorbed gold nanoparticles were functionalized with 4-aminobenzenethiol. This molecular linker attached additional gold nanoparticles to the ‘parent' gold nanoparticle, forming small nanoparticle aggregates. The optical absorption spectrum of these clusters differed from that of gold colloid in a manner consistent with plasmon–plasmon interactions between the gold nanoparticles.     

Investigation of the core-shell interface in gold@silica nanoparticles: a silica imprinting approach

The nature of the self-assembled core-shell interface in gold@silica nanoparticles synthesized via a 3-aminopropyltrimethoxysilane (APTMS) route is investigated using materials synthesis as a sensitive tool for elucidating interfacial composition and organization. Our approach involves condensation of the gold@silica nanoparticles within a silica framework for synthesis of a composite gold-silica material containing approximately 30 wt % gold. This material contains one of the highest gold loadings reported, but maintains gold core isolation as ascertained via a single surface plasmon resonance absorption band frequency corresponding to that of gold nanoparticles in dilute aqueous solution. The immobilized gold cores are subsequently etched using cyanide anion for the synthesis of templated porosity, which corresponds to the space that was occupied by the gold. Characterization of immobilized amines is performed using probe molecule binding experiments, which demonstrate a lack of accessible amines after gold removal. Solid-state 13C CPMAS NMR spectroscopy on these materials demonstrates that the amount of amine immobilization must be less than 10% of the expected yield, assuming that all of the APTMS becomes bound to the gold nanoparticle template. These results require a core-shell interface in the gold@silica nanoparticles that is predominantly occupied by inorganic silicate species, such as Si-O-Si and Si-OH, rather than primary amines. Such a result is likely a consequence of the weak interaction between primary amines and gold in aqueous solution. Our method for investigating the core-shell interface of gold@silica nanoparticles is generalizable for other interfacial structures and enables the synthesis of bulk imprinted silica using colloidal templates.     

基于金纳米粒子的等离子体共振吸收测定阿莫西林

在pH=1.89的Britton-Robinson（BR）缓冲溶液中,阿莫西林与氯金酸反应生成金纳米粒子,在537和720 nm产生了特征等离子体共振吸收信号,其537 nm处的吸收强度与阿莫西林浓度在一定范围内呈线性关系,据此建立了基于金纳米粒子的等离子体共振吸收测定阿莫西林的方法。 在优化条件下（pH=1.89,反应温度65 ℃,反应时间40 min）,测定阿莫西林的线性范围为2.0×10-6~3.6×10-5 mol/L,检出限为1.3×10-7 mol/L。 该方法用于合成样品中阿莫西林的测定,回收率在90.4%~103.2%之间,RSD小于4.6%,将所建立的方法用于2个厂家生产的阿莫西林胶囊中阿莫西林含量测定,并与HPLC法对比,结果满意。     

金纳米线阵列制备及其光谱特性

利用电化学沉积方法在重离子径迹模板中制备出直径从45 nm到200 nm, 长径比达700的金纳米线阵列, 利用扫描电子显微镜(SEM)和X射线衍射(XRD)对所制备金纳米线的形貌及晶体结构进行分析, 结果表明, 在1.5 V(无参比电极)沉积电压下所制备出的直径为200 nm金纳米线沿[100]晶向具有较好择优取向. 利用紫外-可见光谱(UV-Vis)对镶嵌在透明模板中平行排列的金纳米线阵列光学特性进行研究, 发现金纳米线直径为45 nm时, 其紫外可见光谱在539 nm处有强烈吸收峰, 随着金纳米线直径增加, 吸收峰红移, 当金纳米线直径达到200 nm时, 其吸收峰峰位移至700 nm. 结合金纳米颗粒相关表面等离子体共振吸收效应对实验结果进行了讨论.     

Ultrafast electron relaxation dynamics in coupled metal nanoparticles in aggregates

We report the effect of aggregation in gold nanoparticles on their ultrafast electron-phonon relaxation dynamics measured by femtosecond transient absorption pump-probe spectroscopy. UV-visible extinction and transient absorption of the solution-stable aggregates of gold nanoparticles show a broad absorption in the 550-700-nm region in addition to the isolated gold nanoparticle plasmon resonance. This broad red-shifted absorption can be attributed to contributions from gold nanoparticle aggregates with different sizes and/or different fractal structures. The electron-phonon relaxation, reflected as a fast decay component of the transient bleach, is found to depend on the probe wavelength, suggesting that each wavelength interrogates one particular subset of the aggregates. As the probe wavelength is changed from 520 to 635 nm across the broad aggregate absorption, the rate of electron-phonon relaxation increases. The observed trend in the hot electron lifetimes can be explained on the basis of an increased overlap of the electron oscillation frequency with the phonon spectrum and enhanced interfacial electron scattering, with increasing extent of aggregation. The experimental results strongly suggest the presence of intercolloid electronic coupling within the nanoparticle aggregates, besides the well-known dipolar plasmon coupling.     

Plasmonic enhancement of gold nanoparticles on photocycloreversion reaction of diarylethene derivatives depending on particle size, distance from the particle surface, and irradiation wavelength

We newly synthesized various sized gold nanoparticles covered with photochromic polymers consisting of diarylethenes with various structures to investigate an effect of the gold nanoparticles on the photocycloreversion reaction of the diarylethene chromophores upon irradiation with visible light. The gold nanoparticles covered with the photochromic polymers exhibited reversible changes in localized surface plasmon resonance (LSPR) absorption along with the photochromic reaction depending on the diameter of the particle, the distance between the gold surface and the chromophore, and the structure of the diarylethene chromophore. The rate of the photocycloreversion reaction of the chromophores around the particle was enhanced by the gold nanoparticles and the degree of the enhancement was affected by the diameter of the particle and the distance from the gold surface, while a structural difference in the diarylethene chromophore had no effect on the degree of the enhancement. The larger enhancement of the photocycloreversion reaction was observed by irradiation at longer wavelength side than visible light corresponding to the LSPR frequency.