Ferritin as a photocatalyst and scaffold for gold nanoparticle synthesis

The ferrihydrite mineral core of ferritin is a semi-conductor capable of catalyzing oxidation/reduction reactions. This report shows that ferritin can photoreduce AuCl₄ ⁻ to form gold nanoparticles (AuNPs). An important goal was to identify innocent reaction conditions that prevented formation of AuNPs unless the sample was illuminated in the presence of ferritin. TRIS buffer satisfied this requirement and produced AuNPs with spherical morphology with diameters of 5.7 ± 1.6 nm and a surface plasmon resonance (SPR) peak at 530 nm. Size-exclusion chromatography of the AuNP–ferritin reaction mixture produced two fractions containing both ferritin and AuNPs. TEM analysis of the fraction close to where native ferritin normally elutes showed that AuNPs form inside ferritin. The other peak eluted at a volume indicating a particle size much larger than ferritin. TEM analysis revealed AuNPs adjacent to ferritin molecules suggesting that a dimeric ferritin–AuNP species forms. We propose that the ferritin protein shell acts as a nucleation site for AuNP formation leading to the AuNP-ferritin dimeric species. Ferrihydrite nanoparticles (~10 nm diameter) were unable to produce soluble AuNPs under identical conditions unless apo ferritin was present indicating that the ferritin protein shell was essential for stabilizing AuNPs in aqueous solution.     

Phyllanthin-assisted biosynthesis of silver and gold nanoparticles: a novel biological approach

Abstract  The anisotropic gold and spherical–quasi-spherical silver nanoparticles (NPs) were synthesized by reducing aqueous chloroauric acid (HAuCl₄) and silver nitrate (AgNO₃) solution with the extract of phyllanthin at room temperature. The rate of reduction of HAuCl₄ is greater than the AgNO₃ at constant amount of phyllanthin extract. The size and shape of the NPs can be controlled by varying the concentration of phyllanthin extract and thereby to tune their optical properties in the near-infrared region of the electromagnetic spectrum. The case of low concentration of extract with HAuCl₄ offers slow reduction rate along with the aid of electron-donating group containing extract leads to formation of hexagonal- or triangular-shaped gold NPs. Transmission electron microscopy (TEM) analysis revealed that the shape changes on the gold NPs from hexagonal to spherical particles with increasing initial concentration of phyllanthin extract. The Fourier transform infrared spectroscopy and thermogravimetric analyses reveal that the interaction between NPs and phyllanthin extract. The cyclic voltammograms of silver and gold NPs confirms the conversion of higher oxidation state to zero oxidation state. Graphical abstract  Anisotropic gold and silver nanoparticles were synthesized by a simple procedure using phyllanthin extract as reducing agent. The rate of bioreduction of AgNO₃ is lower than the HAuCl₄ at constant concentration of phyllanthin extract. The required size of the nanoparticles can be prepared by varying the concentration of phyllanthin with AgNO₃ and HAuCl₄.      

Surface-enhanced plasmon splitting in a liquid-crystal-coated gold nanoparticle

We show that, when a gold nanoparticle is coated by a thin layer of nematic liquid crystal, the nanoparticle surface has a strong effect on the director orientation, but, surprisingly, this deformation can enhance the surface plasmon splitting. We consider three plausible liquid crystal director configurations in zero electric field: boojum pair (north-south pole configuration), baseball (tetrahedral), and homogeneous. From the discrete dipole approximation, we find that the surface plasmon splitting is largest for the boojum pair, and this result is in good agreement with experiment.     

Ultrafast nonlinear spectroscopy of a single silver nanoparticle

The time‐domain nonlinear spectroscopy of a single silver nano‐object is investigated by combining the spatial modulation linear spectroscopy technique with a high‐sensitivity femtosecond pump–probe setup. The investigated single nanoparticle is first optically characterized for size and shape via quantitative measurement of its linear absorption spectrum, and time‐resolved nonlinear pump‐probe measurements are subsequently performed on the same particle. The breathing mode period of a single nanoparticle measured in the time domain is found to be in good agreement with that inferred by the optically deduced particle characteristics, opening the way of full optical investigation of the acoustic response of the characterized single nanoparticles. Copyright © 2011 John Wiley & Sons, Ltd.     

Photoemission electron microscopy of a plasmonic silver nanoparticle trimer

Anodic aluminum oxide (AAO) films with different porosities were fabricated on the surfaces of InGaN/GaN multiple quantum wells (MQWs). We measured the photoluminescence spectra of these samples and then calculated the light extraction enhancement factors (E). It was found that the light extraction of the MQWs with the AAO films has been greatly enhanced compared to the area without AAO coverage. The maximum value of E reaches 3.5 at a certain wavelength and 2.29 in the integral intensity. The increase of E with the decrease of the porosities demonstrates that the nano-hole structure in the AAO films plays an important role in enhancing the light extraction efficiency.     

Polymer-stabilized colloidal gold: a convenient method for the synthesis of nanoparticles by a UV-irradiation approach

This study describes a simple and convenient method for the preparation of polymer-stabilized colloidal gold by means of an ultra-violet (UV) irradiation technique. Methoxy polyethylene glycol (MPEG) acts as the reducing agent in the presence of the UV irradiation towards gold ions and also acts as the stabilizer of gold particles. The gradual broadening of the UV-visible spectra of the stabilized gold system reflects the formation of larger particles with a longer period of exposure to the UV radiation. PACS 87.20.Dd; 81.16.Hc; 81.07.-b; 78.67.-n; 82.35.Np     

Self‐assembled silver nanoparticle monolayer on glassy carbon: an approach to SERS substrate

In this paper, the fabrication of an active surface‐enhanced Raman scattering (SERS) substrate by self‐assembled silver nanoparticles on a monolayer of 4‐aminophenyl‐group‐modified glassy carbon (GC) is reported. Silver nanoparticles are attached to the substrate through the electrostatic force between the negatively charged silver nanoparticles and the positively charged 4‐aminophenyl groups on GC. The active SERS substrate has been characterized by means of tapping‐mode atomic force microscopy (AFM), indicating that large quantities of silver nanoparticles are uniformly coated on the substrate. Rhodamine 6G (R6G) and p‐aminothiophenol (p‐ATP) are used as the probe molecules for SERS, resulting in high sensitivity to the SERS response, with the detection limit reaching as low as 10⁻⁹ M . This approach is easily controlled and reproducible, and more importantly, can extend the range of usable substrates to carbon‐based materials for SERS with high sensitivity. Copyright © 2007 John Wiley & Sons, Ltd.     

Combinatorial study of a gold nanoparticle infusion process in a polymer film

A novel two-step process is described for infusion of gold nanoparticles (5–20 nm typical diameter) into a polymer film. The technique is demonstrated for the first time in a thermoplastic polyurethane elastomer (TPU). An amine-functional monomer, 2-(diethylamino)ethyl methacrylate, and a free-radical photoinitiator are infused into the surface of the TPU, followed by photopolymerization. An amine-functional semi-interpenetrating network (SIPN) is created within a shallow (~100 μm) surface layer. In the second step, a gold salt, HAuCl₄·3H₂O, is infused into the SIPN from a ternary solvent mixture, and redox reaction with the immobilized amine functional groups produces Au⁰ nanoparticles. Combinatorial processing is conducted to visualize the interdependent effects of two variables, monomer soak time (t ₁) and gold salt solution soak time (t ₂). Combinatorial infusion is accomplished by creating orthogonal gradients in t ₁ and t ₂ in a square TPU plate, allowing examination of sample color, particle size, and polydispersity over a wide range of parameter space. Small angle X-ray scattering (SAXS) is employed as non-invasive means to characterize the Au⁰ particles at three locations in the plate. SAXS measurements are validated by TEM analysis of Au⁰ particle size in a reference sample. A rationale is developed for changing particle size and polydispersity through variation of simple process parameters.     

Dispersion and rheology of surfactant-mediated silver nanoparticle suspensions

Polycrystalline silver (Ag) nanoparticles were dispersed in solvent mixtures consisting of 2-butoxyethyl acetate (BCA) and diethylene glycol monoethyl ether acetate (CA) in a BCA:CA weight ratio of 5:1. Three commercially available polymeric surfactants were used, and the gravitational sedimentation, agglomerate-size distribution, isothermal adsorption, and rheological behavior of the nanoparticle suspensions were examined. One of the surfactants (hereafter termed 9250) was found effective in stabilizing the Ag nanoparticle suspensions. Both the adsorption isotherm and the Fourier transform infrared spectroscopy revealed the preferential adsorption of the 9250 surfactant molecules on the nanoparticle surface, forming a Langmuir-type monolayer adsorption in the given solvents so that a steric stabilization was rendered. An optimal surfactant concentration of 5 wt.% (in terms of the solids weight) was determined experimentally. In addition, the Ag suspensions with a broad range of solids concentration (? = 1-16 vol.%) showed a shear-thinning flow character over a shear-rate range from 1 to 4000 s⁻¹, revealing that an attractive interparticle interaction was operative. Relative viscosity (η_r) of the nanoparticle suspensions deviated from the linearity when ? was greater than ∼10 vol.%; at which, the attractive potential began to dominate the interparticle interactions. This η_r-? dependence was compared with various existing models and the (viscosity) predictive capability of the models was discussed.     

Nonlinear optical behaviours in a silver nanoparticle array at different wavelengths

The optical nonlinearities of an Ag nanoparticle array are investigated by performing the Z-scan measurements at the selected wavelengths (400, 600, 650, and 800 nm). The nonlinear refraction index in the resonant region (around 400 nm) exhibits a significant enhancement by two orders compared with that in the off-resonant region (around 800 nm)), and exhibits an sign alternation of the resonant nonlinear absorption, which results in a negligible nonlinear absorption at a certain excitation intensity. Moreover, a low degree of nonlinear absorption was measured at the edges of the resonant region (600 and 650 nm), which is attributed to the competition of the saturated absorption and the two-photon absorption processes.     

Nonlinear optical behaviors in a silver nanoparticle array at different wavelengths

The optical nonlinearities of an Ag nanoparticle array are investigated by performing Z-scan measurements at the selected wavelengths (400, 600, 650, and 800 nm). The nonlinear refraction index in the resonant region (around 400 nm) exhibits a significant enhancement by two orders compared with that in the off-resonant region (around 800 nm)), and exhibits an sign alternation of the resonant nonlinear absorption, which results in a negligible nonlinear absorption at a certain excitation intensity. Moreover, a low degree of nonlinear absorption was measured at the edges of the resonant region (600 and 650 nm), which is attributed to the competition of the saturated absorption and the two-photon absorption processes.     

Femtosecond pump-probe investigation of ultrafast silver nanoparticle deformation in a glass matrix

Single-color femtosecond pump-probe experiments were performed to investigate the time dependence of laser-induced ultrafast desorption and deformation processes of silver nanoparticles in glass. After laser excitation at wavelengths close to the surface plasmon resonance, transient extinction changes were found to exhibit dynamics on quite different time scales ranging from sub-picoseconds to some hundred ps. The slowest observed decay component is identified as characteristic for the deformation/desorption processes. Possible mechanisms for these processes are discussed. Received: 3 April 2000 / Revised version: 3 July 2000 / Published online: 20 September 2000     

重力对金纳米颗粒在生物膜表面吸附影响的荧光研究

纳米颗粒在生物膜表面的吸附行为是纳米生物技术领域的重要问题. 采用正、倒置实验, 通过荧光显微镜定量研究了重力对金纳米颗粒在支撑磷脂膜表面吸附的影响. 研究发现, 颗粒尺寸决定其在顶或底层支撑膜表面吸附的差异性. 吸附量的差异与颗粒的沉淀速率和扩散速率之比的对数呈线性关系. 粒径小于14 nm时, 不考虑重力在吸附时的影响; 粒径大于176 nm时, 重力在吸附中占主导地位. 为药物载体研究和理解颗粒－生物膜相互作用提供参考.     

Surface plasma waves in silver and gold

The dispersion curves for surface plasma waves (SPW) in Ag have been determined from calculated reflectivity minima as exhibited by attenuated total reflection (ATR spectra) for the prism-air-metal (PAM) configuration and from the direct calculation of the dispersion relation for the same configuration. The dispersion curves for Au have been determined by measuring the ATR spectra for the prism-dielectric-metal (PDM) configuration, by calculating the ATR spectra from published optical constants and from the direct calculation of the despersion relation for the PDM configuration. We have found two general types of solutions from the direct calculation of the dispersion relation for both configurations. The two solutions are the surface or Brewster modes and the virtual modes. The characteristics of both modes are discussed. The effect of electronic damping upon the dispersion curves for Ag which exhibits low electronic damping and Au which exhibits moderate electronic damping is demonstrated. Finally the perturbing effect of the dielectric (referred herein as dielectric shift) upon the displacement of the dispersion curves to higher wave number for the PAM configuration for Ag and for the PDM configuration for Au is shown.     

A novel approach to metal and metal oxide nanoparticle synthesis: the oil-in-water microemulsion reaction method

A novel and straightforward approach, based on oil-in-water (o/w) microemulsions, was developed for the synthesis of inorganic nanoparticles at ambient conditions. It implies the use of organometallic precursors dissolved in nanometre-scale oil droplets of o/w microemulsions. Addition of reducing or oxidizing/precipitating agents results in the formation of metallic or metal oxide nanoparticles, respectively. Nonionic o/w microemulsion systems were chosen, and several key compositions were selected for nanoparticle synthesis at 25 °C. High Resolution Electron Microscopy revealed that small nanoparticles of metals (Pt, Pd and Rh) and nanocrystalline metal oxide (cerium (IV) oxide with cubic type crystalline structure confirmed by XRD), of less than 7 nm can be obtained in mild conditions.     

电感耦合等离子体质谱法测定铜矿区20种植物中的金银

采用灰化-王水处理试样,选取103 Rh和203 Tl作为测定107 Ag、109 Ag和197 Au的内标元素,建立了电感耦合等离子体质谱法测定铜矿区栓皮栎等20种植物中金和银的方法。所建立方法用于不同矿区植物样品的分析,相对标准偏差(n=5)为9.05%～0.85%,加标回收率在93.6%～101.6%之间,Au和Ag检出限分别为0.048和1.06ng.g-1。该方法简便、准确,适用于铜矿区植物中金和银的测定。测定结果表明,矿区中金和银含量因不同植物而存在较大差异,变动范围为Au:0.18～0.99ng.g-1,Ag:282～2 150ng.g-1,其中凤尾蕨、芒萁和长叶实蕨中Ag具备地球化学异常特征,可作为找矿有效指示的植物。     

Laser sintering of silver nanoparticle thin films: microstructure and optical properties

We present a method for the sintering of silver (Ag) nanoparticle thin films by millisecond pulsed laser irradiation. The microstructure of sintered thin films and sintering behaviors of nanoparticles were systematically investigated in this paper. Absorption spectra of sintered thin films showed blue-shifted surface plasmon resonances (SPR) from 500 nm to 480 nm and red-shifted from 480 nm to 550 nm when laser power was varied from 100 W to 140 W and from 140 W to 200 W, respectively. This indicates a new technique to control light absorption through joining nanoparticles with laser sintering. According to theoretical calculations based on a heat diffusion model, the melting temperature of these Ag nanoparticles was estimated to be 440 °C during laser irradiation.     

Measurement of the complex dielectric constant of a single gold nanoparticle

A differential interference contrast microscopy technique that employs a photonic crystal fiber as a white-light source is used to measure both the real and the imaginary part of the complex dielectric constant of single 10 and 15 nm gold nanoparticles over a wavelength range of 480 to 610 nm. Noticeable deviations from bulk gold measurements are observed at short wavelengths and for individual particles even after taking into account finite-size surface damping effects.     

Adsorption of purpald SAMs on silver and gold electrodes: a Raman mapping study

The adsorption modes of 4‐amino‐3‐hydrazino‐5‐mercapto‐1,2,4‐trizole (purpald) self‐assembled monolayers (SAMs) formed on SERS‐active silver and gold electrodes were comparatively studied using surface‐enhanced Raman scattering (SERS), and the self‐assembling procedures were investigated by the Raman mapping technique. Purpald SAMs adopted a titled orientation with S, N2 atoms anchoring to the silver electrode and the  N7H₂ close to the surface, whereas purpald stood up on the gold electrode through S, N5 atoms and with  N8H₂ adjacent to the surface. The density functional theory (DFT) at the level of B3LYP was performed to help explain their different adsorption behaviors on the silver and gold electrodes. Copyright © 2006 John Wiley & Sons, Ltd.