Optical Properties of Ag and Au Nanoparticles Dispersed within the Pores of Monolithic Mesoporous Silica

The optical absorption of silver and gold nanoparticles dispersed within the pores of monolithic mesoporous silica upon annealing at elevated temperatures has been investigated. With decreasing particle size, the surface plasmon resonance position of the particles blue-shifts first and then red-shifts for silver/silica samples, but only red-shifts for gold/silica samples. This size evolution of the resonance position is completely different from that previously reported for fully embedded particles. We assume a local porosity at the particle/matrix interface, such that free surface of particles within the pores may be in contact with ambient air, and present a two-layer core/shell model to calculate the optical properties. These calculations also consider deviations from the optical constants of bulk matter to account for corresponding effects below about 10 nm particle size. From the good agreement between experimental results and model calculations, we conclude a peculiar particle/ambience interaction dominating the size evolution of the resonance. Because of the difference of core electron structure, the relative importance of the effects of local porosity and free surface, respectively, are different for silver and gold. For silver, the effect of the local porosity is stronger, but for gold the opposite is found.     

Synthesis and photo physical properties of Au @ Ag (core @ shell) nanoparticles disperse in poly vinyl alcohol matrix

Synthesis of core @ shell (Au @ Ag) nanoparticle with varying silver composition has been carried out in aqueous poly vinyl alcohol (PVA) matrix. Core gold nanoparticle (~15 nm) has been synthesized through seed-mediated growth process. Synthesis of silver shell with increasing thickness (~1–5 nm) has been done by reducing Ag⁺ over the gold sol in the presence of mild reducing ascorbic acid. Characterization of Au @ Ag nanoparticles has been done by UV–Vis, High resolution transmission electron microscope (HRTEM) and energy dispersive X-ray (EDX) spectroscopic study. The blue shift of surface plasmon resonance (SPR) band with increasing mole fraction of silver has been interpreted due to dampening of core, i.e. Au SPR by Ag. The dependence of nonlinear optical response of spherical core @ shell nanoparticles has been investigated as a function of relative composition of each metal. Simulation of SPR extinction spectra based on quasi-static theory is done. A comparison of our experimental and the simulated extinction spectra using quasi-static theory of nanoshell suggests that our synthesized bimetallic particles have core @ shell structure rather than bimetallic alloy particles.     

Acoustic cavitation for engineering of gold sols in silver nitrate solutions

Binary gold-silver nanostructures of preformed gold nanoparticles (25nm) in silver nitrate solutions are produced by a two step sonication (20kHz). Ultrasonic treatment of gold-silver mixtures is carried out in the presence of sodium dodecyl sulfate in water or 2-propanol, and poly(vinyl pyrrolidone) in ethylene glycol solutions. Gold-silver nano-worms, which consist of ripened gold particles connected by ultrasonically reduced silver, are formed after 1h of sonication in the presence of sodium dodecyl sulfate aqueous solution. In 2-propanol bimetallic nano-worms have a well defined core-shell structure. Polygonal alloy nanoparticles with gold as a core material and a silver shell are produced after 180min of sonication in the presence of poly(vinyl pyrrolidone) in ethylene glycol solution. Bimetallic gold-silver nanostructures have defected face centered cubic structure and represent polycrystals with a large number of crystallites randomly oriented. For the first time, the mechanism of gold particle design by ultrasound is examined in detail. The role of additives (sodium dodecyl sulfate, polyvinyl pyrrolidone, ethylene glycol and 2-propanol) as reductants of silver at the gold contact surface or stabilizers of particles is highlighted.     

Plasmonics properties of trimetallic Al@Al2O3@Ag@Au and Al@Al2O3@AuAg nanostructures

Bimetallic and trimetallic nanoparticles have attracted significant attention in recent times due to their enhanced electrochemical and catalytic properties compared to monometallic nanoparticles. The numerical calculations using Mie theory has been carried out for three-layered metal nanoshell dielectric–metal–metal (DMM) system consisting of a particle with a dielectric core (Al@Al₂O₃), a middle metal Ag (Au) layer and an outer metal Au (Ag) shell. The results have been interpreted using plasmon hybridization theory. We have also prepared Al@Al₂O₃@Ag@Au and Al@Al₂O₃@AgAu triple-layered core–shell or alloy nanostructure by two-step laser ablation method and compared with calculated results. The synthesis involves temporal separations of Al, Ag, and Au deposition for step-by-step formation of triple-layered core–shell structure. To form Al@Ag nanoparticles, we ablated silver for 40 min in aluminium nanoparticle colloidal solution. As aluminium oxidizes easily in water to form alumina, the resulting structure is core–shell Al@Al₂O₃. The Al@Al₂O₃ particle acts as a seed for the incoming energetic silver particles for multilayered Al@Al₂O₃@Ag nanoparticles is formed. The silver target was then replaced by gold target and ablation was carried out for different ablation time using different laser energy for generation of Al@Al₂O₃@Ag@Au core–shell or Al@Al₂O₃@AgAu alloy. The formation of core–shell and alloy nanostructure was confirmed by UV–visible spectroscopy. The absorption spectra show shift in plasmon resonance peak of silver to gold in the range 400–520 nm with increasing ablation time suggesting formation of Ag–Au alloy in the presence of alumina particles in the solution.     

Flow Synthesis of Plasmonic Gold Nanoshells via a Microreactor

Gold nanoshells with tunable surface plasmon resonances are a promising material for optical and biomedical applications. They are produced through seed‐mediated growth, in which gold nanoparticles (AuNPs) are seeded on the core particle surface followed by growth of the gold seeds into a shell. However, synthetic gold nanoshell production is typically a multistep, time‐consuming batch‐type process, and a simple and scalable process remains a challenge. In the present study, a continuous flow process for the seed‐mediated growth of silica–gold nanoshells is established by exploiting the excellent mixing performance of a microreactor. In the AuNP‐seeding step, the reduction of gold ions in the presence of core particles in the microreactor enables the one‐step flow synthesis of gold‐decorated silica particles through heterogeneous nucleation. Flow shell growth is also realized using the microreactor by selecting an appropriate reducing agent. Because self‐nucleation in the bulk solution phase is suppressed in the microreactor system, no washing is needed after each step, thus enabling the connection of the microreactors for the seeding and shell growth steps into a sequential flow process to synthesize gold nanoshells. The established system is simple and robust, thus making it a promising technology for producing gold nanoshells in an industrial setting.     

Fabrication of magnetic gold nanorod particles for immunomagnetic separation and SERS application

The preparation and application of rod-shaped core–shell structured Fe₃O₄–Au nanoparticles for immunomagnetic separation and sensing were described for the first time with this study. To synthesize magnetic gold nanorod particles, the seed-mediated synthetic method was carried out and the resulting nanoparticles were characterized with transmission electron microscopy (TEM), ultraviolet visible spectroscopy (UV–Vis), energy-dispersive X-ray (EDX), and X-ray diffraction (XRD). Magnetic properties of the nanoparticles were also examined. Characterization of the magnetic gold nanorod particles has proven that the resulting nanoparticles were composed of Fe₃O₄ core and the gold shell. The rod-shaped gold-coated iron nanoparticles have an average diameter of 16 ± 2 nm and an average length of about 50 ± 5 nm (corresponding aspect ratio of 3). The saturation magnetization value for the magnetic gold nanorod particles was found to be 37 emu/g at 300 K. Rapid and room temperature reaction synthesis of magnetic gold nanorod particles and subsequent surface modification with E. coli antibodies provide immunomagnetic separation and SERS application. The analytical performance of the SERS-based homogenous sandwich immunoassay system with respect to linear range, detection limit, and response time is also presented.     

金纳米球壳光学吸收的Mie理论分析

基于Mie散射理论研究了金壳厚度变化、内核尺寸变化及内核介质变化下金纳米球壳的吸收光谱.研究发现,随着金壳厚度的增加,颗粒光学吸收增加到最大值后逐渐降低;随着内核尺寸逐渐增加,金壳颗粒的光学吸收最大值逐渐减小.此外,还发现随着内核介电常数的增大,颗粒的光学吸收逐渐减弱,当内核为空心时,吸收最强.利用等离激元杂化理论及自由电子和振荡电子变化的竞争机制对上述现象进行了理论分析. 关键词： 金纳米球壳 等离激元共振 吸收光谱     

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     

复合金属粒子散射强度分布的计算与分析

根据Mie散射理论,对金银复合粒子的散射强度和偏振度进行了数值计算与理论分析,得到了散射强度、偏振度与散射角、入射波长及核壳大小之间的关系。结果表明,入射波长越大,前向散射越强,易出现线偏振光;而核壳半径越大,背向散射越弱,易出现退偏振现象。该结论对金银复合材料光学特性方面的开发和应用提供理论参考。     

NaCl structure in a mixture of silica and gold sols

The formation of an NaCl structure in a mixture of a monodisperse silica sol with particle diameter of 5300 A and a gold sol with average particle size of 800 A is described. The mixture was left still for a month, and the particles settled to form a dense layer at the bottom, where phase separation appeared. In the ordered phase only gold particles were observed microscopically as bright spots at their individual lattice points, being arranged in hexagonal or in square pattern. From the distance between the particles in the square pattern and hexagonal pattern, the lattice type for gold particles was concluded to be fcc. Further, it was known that four gold particles forming a square hold one silica particle in its center. On these grounds, the entire lattice was concluded to be of the NaCl-type.     

Structural and Optical Properties of Gold/Silica “Mushroom” Particles Prepared by Interfacial Templating

Complex shaped nanoparticles featuring structural or surface chemical patchiness are of special interest in both fundamental and applied research areas. This study reports the preparation and optical properties of gold/silica “mushroom” nanoparticles, where a gold particle is only partially covered by the silica cap. The synthetic approach allows precise control over the particle structure. The interfacial preparation method relies on partially embedding the gold particles in a polystyrene layer that masks the immersed part of the gold particle during silica shell growth from an aqueous solution. By adjusting sacrificial polystyrene film thickness and silica growth time, precise control over the coverage and cap thickness can be achieved. Correlative electron microscopy and single particle scattering spectroscopy measurements underline the high precision and reproducibility of the method. The good agreement between the measured and simulated single particle spectra supported by near‐field calculations indicates that the observed changes in the dipolar plasmon resonance are influenced by the extent of coverage of the gold core by the silica cap. The straightforward methods readily available for gold and silica surface modification using range of different (bio)molecules make these well‐defined nanoscale objects excellent candidates to study fundamental processes of programmed self‐assembly or application as theranostic agents.     

A Correlative Analysis of Gold Nanoparticles Internalized by A549 Cells

Fluorescently labeled nanoparticles are widely used to investigate nanoparticle cell interactions by fluorescence microscopy. Owing to limited lateral and axial resolution, nanostructures (<100 nm) cannot be resolved by conventional light micro­scopy techniques. Especially after uptake into cells, a common fate of the fluorescence label and the particle core cannot be taken for granted. In this study, a correlative approach is presented to image fluorescently labeled gold nanoparticles inside whole cells by correlative light and electron microscopy (CLEM). This approach allows for detection of the fluorescently labeled particle shell as well as for the gold core in one sample. In this setup, A549 cells are exposed to 8 nm Atto 647N‐labeled gold nanoparticles (3.3 × 10⁹ particles mL^?1, 0.02 μg Au mL^?1) for 5 h and are subsequently imaged by confocal laser scanning microscopy (CLSM) and transmission electron microscopy (TEM). Eight fluorescence signals located at different intracellular positions are further analyzed by TEM. Five of the eight fluorescence spots are correlated with isolated or agglomerated gold nanoparticles. Three fluorescence signals could not be related to the presence of gold, indicating a loss of the particle shell.     

Features of the microstructure of gold nanoparticles inside cavities of cucurbit[7]uril according to XAFS spectra

The Au L ₃ X-ray absorption fine structure (XAFS) spectra have been measured for gold nanoparticles with the calibrated size d _Au ～ 1 nm in the cavities of cucurbit[7]uril molecules. The features of their electronic structure and microstructure have been characterized. It has been found that gold clusters in cavities of cucurbit[7]uril are characterized by smaller (by 0.01–0.02 Å) interatomic distances and a noticeably larger (by a factor of 3 at 12 K) Debye-Waller factor as compared to bulk gold. Analysis of the experimental results and their comparison with the model calculations show that the special properties of atoms on the surface of small metal (gold) particles are not determined by their position at the vertices and edges of small clusters; they are likely attributed to the structural disorder, deformations, and stresses, which increase with a decrease in the size of the particles.     

光照法在玻璃基底上原位生长金纳米结构及其光谱性质

 以硅烷化后吸附粒径小于10 nm的金种子的玻璃片为基底,聚乙烯吡咯烷酮为还原剂,在荧光灯照射条件下还原氯金酸,制备出表面具有金纳米粒子聚集结构的基底。用原子力显微镜、扫描电镜、X射线衍射、吸收和荧光光谱研究了基底的性质。结果表明：随着光照时间增加至20 h,金种子长大为平均粒径140 nm的不规则状多晶粒子,且出现双层粒子堆叠。基底的吸收光谱上出现了由金粒子的表面等离子体激元偶极子耦合引发的强烈吸收峰,随着粒子粒径增大,耦合峰在600~800 nm波段内连续红移升高,表明耦合程度不断增强。在223 nm紫外光的激发下,基底的荧光光谱上在405 nm处出现发射峰,是由金粒子表面激发电子和空穴的复合辐射造成的,发光强度随着基底上粒子平均尺度增加而减弱。     

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 magnetism of Co:CoO core–shell nanoclusters

Transmission electron microscopy (TEM) and electron diffraction (ED) are used to investigate the nanostructures of two ensembles of Co:CoO core–shell particles. TEM images show that particles of size about 12 nm are almost fully oxidized, while particles with size about 18 nm have a core–shell structure where a Co core is surrounded by a shell of CoO. ED simulation confirms that the larger particles have an fcc-structured Co core and a rock-salt CoO shell structure, while the smaller particles mostly have the rock-salt CoO structure. The core–shell structure is responsible for the unusual magnetic properties of the Co:CoO nanoclusters, especially the occurrence of inverted hysteresis loops (proteresis), but previous research has been indirect, largely based on magnetic measurements and on a cross-comparison with granular materials. Our measurements show that the structures have ferromagnetic fcc Co cores of varying sizes down to 1 nm which are surrounded by antiferromagnetic rock-salt CoO shells. The core radii obtained from the TEM pictures are used to estimate the exchange interactions responsible for proteresis and to pinpoint the core-size window in which proteresis occurs.     

The intrinsic structure of spherical particles of opal

The intrinsic structure of spherical SiO₂ particles synthesized by hydrolysis of tetraethyl orthosilicate in an alcohol-water-ammonia medium was studied using transmission electron microscopy. It was established that the relatively large spherical silica particles were “tertiary” structures made up of smaller spherical particles (“ secondary” particles), which in turn consisted of even smaller primary spherical particles 5–10 nm in diameter. It was shown that, under the experimental conditions, the large SiO₂ particles can contain a central core comprising primary particles surrounded by several layers of secondary particles smaller than the core diameter.     

Local density variation of gold nanoparticles in aquatic environments

Gold (Au) nanoparticles are widely used in diagnosing cancer, imaging, and identification of therapeutic methods due to their particular quantum characteristics. This research presents different types of aqueous models and potentials used in TIP3P, to study the effect of the particle size and density of Au clusters in aquatic environments; so it can be useful to facilitate future investigation of the interaction of proteins with Au nanoparticles. The EAM potential is used to model the structure of gold clusters. It is observed that in the systems with identical gold/water density and different cluster radii, gold particles are distributed in aqueous environment almost identically. Thus, Au particles have identical local densities, and the root mean square displacement (RMSD) increases with a constant slope. However in systems with constant cluster radii and different gold/water densities, Au particle dispersion increases with density; as a result, the local density decreases and the RMSD increases with a larger slope. In such systems, the larger densities result in more blunted second peaks in gold–gold radial distribution functions, owing to more intermixing of the clusters and less FCC crystalline features at longer range, a mechanism that is mediated by the competing effects of gold–water and gold–gold interactions.     

Correlation between structure and optoelectronic properties in a two‐dimensional nanoparticle assembly

The optical properties of two‐dimensional assemblies of metal nanoparticles are strongly influenced by the morphological configuration of the metal particles in the layer. Therefore, we correlate the structural and optical properties of two‐dimensional, hexagonal gold nanoparticle arrays. We characterize the structure of the arrays using grazing‐incidence small angle X‐ray scattering (GISAXS). From the GISAXS pattern, we determine the size of the gold particles as well as the lattice spacing of the hexagonal assembly. Based upon these parameters we calculate the dielectric function of the gold particle array using the Maxwell–Garnett effective medium theory. We further deduce the absorption spectrum which closely follows the measured absorption and photoconductance spectrum. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Y2Si2O7:Eu/SiO2 core shell phosphor particles prepared by flame spray pyrolysis

This paper reports the synthesis of core shell phosphor particles (Y₂Si₂O₇:Eu/SiO₂) produced by flame spray pyrolysis with yttrium and europium nitrates and colloidal silica dispersed precursor solutions. Particles of various structures were produced, including heterogeneous, core shell and non-spherical core shell particles, depending on the synthesis conditions; the ideal core shell structure was obtained under the highest flame temperature and high silicon concentration in the precursor solution. Based on the phase diagram, the formation of the core shell structure was caused by the separation of each component at the liquid phase in the synthesis route. In the energy-dispersive X-ray spectroscopy, yttrium could be detected only at the core part of the particle, while silicon and oxygen could be detected at both the shell and core parts. Under ultraviolet excitation, the ideal core shell particles of Y₂Si₂O₇:Eu showed photoluminescent characteristics. Consequently, it could be concluded that Y₂Si₂O₇:Eu/SiO₂ core shell phosphor particles were successfully synthesized by flame spray pyrolysis.