Electrochromic properties of WO3 thin film onto gold nanoparticles modified indium tin oxide electrodes

Gold nanoparticles (GNPs) thin films, electrochemically deposited from hydrogen tetrachloroaurate onto transparent indium tin oxide (ITO) thin film coated glass, have different color prepared by variation of the deposition condition. The color of GNP film can vary from pale red to blue due to different particle size and their interaction. The characteristic of GNPs modified ITO electrodes was studied by UV-vis spectroscopy, scanning electron microscope (SEM) images and cyclic voltammetry. WO₃ thin films were fabricated by sol-gel method onto the surface of GNPs modified electrode to form the WO₃/GNPs composite films. The electrochromic properties of WO₃/GNPs composite modified ITO electrode were investigated by UV-vis spectroscopy and cyclic voltammetry. It was found that the electrochromic performance of WO₃/GNPs composite films was improved in comparison with a single component system of WO₃.     

An anisotropic snowflake-like structural assembly of polymer-capped gold nanoparticles

Snowflake-like structural assembly of isotropic gold nanoparticles (GNPs) is reported. A modified polyamine method has been employed to synthesize positively charged GNPs in presence of a polymeric metaphosphate. This process yields fascinating dendritic self-assembled morphologies. Structural characterization revealed that there was aggregation of crystalline GNPs. The aggregates of GNPs formed in the initial stage of synthesis are assumed to act as the bulging seeds for final growth of complex morphologies at nanometer to micrometer length scale. Self-assembly of GNPs was found to be greatly influenced by the concentration of gold precursor. Diffusion limited aggregation of GNPs is suggested as the plausible mechanism for this nanoparticle self-organization process.     

Surface enhanced Raman spectroscopic readout on heavy metal ions based on surface self assembly

A new method is reported for detecting heavy metal ions by using the self assembled monolayer (SAM) technique and surface enhanced Raman spectroscopy (SERS). The p‐mercaptobenzoic acid (MBA) served as the SERS readout molecule and the modified tag to attach on the smooth gold substrate as well as the tag of nanoparticles by the SAM method. Two carboxyl groups from MBA molecules which were attached respectively to gold substrate and gold nanoparticles were linked through the heavy metal ions (Cu²⁺, Pb²⁺ and Zn²⁺) as bridge, and thus sandwich structure of ‘MBA modified gold substrate/heavy metal ions/MBA modified gold nanoparticles’ was built for detection. The observation of the oxidation peak of metal nanoparticles from cyclic voltammetry (CV) curve, gold nanoparticles from scanning electron microscopy (SEM) images and SERS signal of MBA from the sandwich structure indicated the existence of heavy metal ions. The difference in the wavenumbers of vibrational modes from MBA in the sandwich structure constructed by different could be used to identify different heavy metal ions. The assembled structure was rinsed by strong chelator of EDTA solution to remove the heavy metal ions from the sandwich structure and thus to obtain a fresh gold substrate modified with MBA for the cyclic detection. Copyright © 2007 John Wiley & Sons, Ltd.     

Electrochemical analysis of gold-coated magnetic nanoparticles for detecting immunological interaction

An electrochemical impedance immunosensor was developed for detecting the immunological interaction between human immunoglobulin (IgG) and protein A from Staphylococcus aureus based on the immobilization of human IgG on the surface of modified gold-coated magnetic nanoparticles. The nanoparticles with an Au shell and Fe oxide cores were functionalized by a self-assembled monolayer of 11-mercaptoundecanoic acid. The electrochemical analysis was conducted on the modified magnetic carbon paste electrodes with the nanoparticles. The magnetic nanoparticles were attached to the surface of the magnetic carbon paste electrodes via magnetic force. The cyclic voltammetry technique and electrochemical impedance spectroscopy measurements of the magnetic carbon paste electrodes coated with magnetic nanoparticles–human IgG complex showed changes in its alternating current (AC) response both after the modification of the surface of the electrode and the addition of protein A. The immunological interaction between human IgG on the surface of the modified magnetic carbon paste electrodes and protein A in the solution could be successfully monitored.     

Biosynthesis of gold nanoparticles using Capsicum annuum var. grossum pulp extract and its catalytic activity

Biological synthesis approach has been regarded as a green, eco-friendly and cost effective method for nanoparticles preparation without any toxic solvents and hazardous bi-products during the process. This present study reported a facile and rapid biosynthesis method for gold nanoparticles (GNPs) from Capsicum annuum var. grossum pulp extract in a single-pot process. The aqueous pulp extract was used as biotic reducing agent for gold nanoparticle growing. Various shapes (triangle, hexagonal, and quasi-spherical shapes) were observed within range of 6–37 nm. The UV–Vis spectra showed surface plasmon resonance (SPR) peak for the formed GNPs at 560 nm after 10 min incubation at room temperature. The possible influences of extract amount, gold ion concentration, incubation time, reaction temperature and solution pH were evaluated to obtain the optimized synthesis conditions. The effects of the experimental factors on NPs synthesis process were also discussed. The produced gold nanoparticles were characterized by transform electron microscopy (TEM), X-ray diffraction (XRD), energy dispersive X-ray (EDS) and Fourier Transform infrared spectroscopy (FTIR). The results demonstrated that the as-obtained GNPs were well dispersed and stable with good catalytic activity. Biomolecules in the aqueous extract were responsible for the capping and stabilization of GNPs.     

Electrosynthesis and characterization of poly aniline/garnet nanoparticles for high-performance electrochemical capacitors

In this work, supercapacitive performance of polyaniline/yttrium aluminum garnet (YAG: Y₃Al₅O₁₂) nanoparticles (PANI/YAGNPs) was studied. YAG nanoparticles were synthesized by pulse electro-deposition method and after that, PANI/YAGNPs electrodeposited on the surface of glassy carbon electrodes through cyclic voltammetry. Morphological studies show that YAG nanoparticles were distributed in the structure of PANI filaments uniformly. XRD and FTIR were used to perform a structural study of materials. Different electrochemical techniques such as cyclic voltammetry (CV), galvano static charge discharge (CD), and impedance spectroscopy (EIS) were used to evaluate the applicability of using PANI/YAGNPs as an active material for supercapacitors. The specific capacitance (SC) of PANI and PANI YAG NPs electrodes calculated using CV technique are 240 and 440 F/g, respectively. Increasing the conductivity and stability of composite electrodes during continuous CD cycles compared to PANI ones are some features of using YAG NPs in the structure of polymer electrodes. Stability of composite electrodes remains about 98% through 1000 continuous cycles whereas the polymeric electrode loses about 91% of its capacitance during this time range.     

Interaction between α-actinin and negatively charged lipids membrane investigated by surface plasmon resonance and electrochemical methods

α-Actinin has been shown to be capable of interacting with some special membrane phospholipids directly, which is important for its function. In this study, hybrid bilayer membranes composed of negatively charged lipids are constructed on the surface plasmon resonance gold substrate and on the gold electrode, respectively, and the interaction between α-actinin and negatively charged lipids membrane is investigated by surface plasmon resonance, cyclic voltammetry and electrochemical impedance spectroscopy methods. α-Actinin is proved to be able to interact with the negatively charged lipids membrane directly. It can also insert at least partly into the membrane or lead to some defect or lesion in the membrane, which increase the permeability of the membrane. This study would bring some insight on the interaction between the α-actinin and the cell membranes in vivo.     

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.     

Hydrogen peroxide biosensor based on gold nanoparticles/thionine/gold nanoparticles/multi-walled carbon nanotubes-chitosans composite film-modified electrode

In this paper, an amperometric electrochemical biosensor for the detection of hydrogen peroxide (H₂O₂), based on gold nanoparticles (GNPs)/thionine (Thi)/GNPs/multi-walled carbon nanotubes (MWCNTs)-chitosans (Chits) composite film was developed. MWCNTs-Chits homogeneous composite was first dispersed in acetic acid solution and then the GNPs were in situ synthesized at the composite. The mixture was dripped on the glassy carbon electrode (GCE) and then the Thi was deposited by electropolymerization by Au-S or Au-N covalent bond effect and electrostatic adsorption effect as an electron transfer mediator. Finally, the mixture of GNPs and horseradish peroxidase (HRP) was assembled onto the modified electrode by covalent bond. The electrochemical behavior of the modified electrode was investigated by scanning electron microscope, cyclic voltammetry and chronoamperometry. This study introduces the in situ-synthesized GNPs on the other surface of the modified materials in H₂O₂ detection. The linear response range of the biosensor to H₂O₂ concentration was from 5 × 10⁻⁷ mol L⁻¹ to 1.5 × 10⁻³ mol L⁻¹ with a detection limit of 3.75 × 10⁻⁸ mol L⁻¹ (based on S/N = 3).     

Single-wall carbon nanotube chemical attachment at platinum electrodes

Self-assembled monolayer (SAM) techniques were used to adsorb 4-aminothiophenol (4-ATP) on platinum electrodes in order to obtain an amino-terminated SAM as the base for the chemical attachment of single-wall carbon nanotubes (SWCNTs). A physico-chemical, morphological and electrochemical characterizations of SWCNTs attached onto the modified Pt electrodes was done by using reflection-absorption infrared spectroscopy (RAIR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and cyclic voltammetry (CV) techniques. The SWNTs/4-ATP/Pt surface had regions of small, medium, and large thickness of carbon nanotubes with heights of 100-200 nm, 700 nm to 1.5 μm, and 1.0-3.0 μm, respectively. Cyclic voltammetries (CVs) in sulfuric acid demonstrated that attachment of SWNTs on 4-ATP/Pt is markedly stable, even after 30 potential cycles. CV in ruthenium hexamine was similar to bare Pt electrodes, suggesting that SWNTs assembly is similar to a closely packed microelectrode array.     

Size-controlled growth of gold nanoparticle-doped carbon foams as sensitive electrochemical sensors for the determination of Pb(II)

A sensitive and selective electrochemical Pb²⁺ sensor consisting of a gold-carbon foam/chitosan/gold (Au-CFs/Chit/Au)-modified electrode was prepared. The electrode was synthesized via an oil-in-water emulsion polymerization and carbonization approach. Phenolic resins were used as a carbon source. HAuCl₄ was used as a gold source and as an acidic catalyst. Melamine was used as a coordination and coupling agent to control the size of the Au nanoparticles (AuNPs). The morphologies and microstructures of the Au-CFs were characterized using scanning electron microscopy, X-ray diffraction, and transmission electron microscopy. The results revealed that the carbon foams contained interconnected macropores with diameters of nearly 5.0 μm and AuNPs with mean diameters of approximately 20.0, 9.0, and 7.0 nm. Brunauer–Emmett–Teller analysis revealed that the biggest surface area is 653.82 m²/g for Au/CFs-7. The electrochemical properties of modified electrodes and their responses to Pb²⁺ were characterized using cyclic voltammetry and differential pulse anodic stripping voltammetry. The influence of the test conditions were studied to optimize operational parameters such as the choice of supporting electrolyte, pH, deposition potential, and deposition time. Under optimal conditions, typical Au/CFs-7-modified gold electrodes exhibited an excellent electrochemical response for Pb²⁺ with a wide linear response range from 0.01 to 1.2 μM, a correlation coefficient of 0.995, and a lower limit of detection of 0.63 nM with deposition time of 180 s (S/N?=?3).     

Self-assembled bilayers based on organothiol and organotrimethoxysilane on zinc platform

This study describes the formation of a bilayer system developed on electrodeposited zinc. In a first step, a monolayer of 11-mercapto-1-undecanol is grafted on zinc, optimization of the conditions of elaboration have been performed. In a second step, organotrimethoxysilane have been grafted on the zinc modified with the hydroxyl terminated self-assembled monolayer (SAM) to finalize the bilayer system. X-ray photoelectron spectroscopy (XPS), polarization modulation-infrared reflection absorption spectroscopy (PM-IRRAS) and contact angle measurements are used to characterize each step of modification. An electrochemical evaluation of the different created systems is carried out by linear sweep voltammetry (LSV), cyclic voltammetry (CV) and scanning vibrating electrode technique (SVET). The impact of the modification of zinc using SAM and self-assembled bilayer (SAB) on the electrochemical activity of the surface is highlighted.     

Electrolytic metal deposition onto chemically modified electrodes

Some general features concerning electrochemical metal deposition onto electrodes modified with self-assembled monolayers (SAMs) of alkanethiols are discussed. Although thiols of various chain length are briefly addressed, special emphasis is placed on copper deposition onto an ethanethiol (C2)-modified Au(111) surface. The short alkanethiol blocks the surface to a great extent but does not completely suppress charge transfer. We have used in situ scanning tunneling microscopy (STM) and cyclic voltammetry (CV) to characterize the structure and the electrochemical behavior of the C2 monolayer in sulfuric acid electrolyte before and after introducing copper ions to the system. The C2 adlayer consists of domains of two different ordered structures. It is shown that the adlayer undergoes a reversible order–disorder transition at potentials slightly negative of 0 V vs. SCE, which testifies to a surprisingly high mobility of the C2 molecules within the SAM. Copper deposition on C2-modified gold electrodes shows significant differences from the same process on the bare electrode. A sharp cathodic peak at -0.18 V vs. SCE is ascribed to the insertion of a Cu monolayer between Au and the organic adlayer. At low overpotentials the Cu deposit exhibits a ramified monatomic high morphology, if the ethanethiol adlayer is dense. Three-dimensional growth starts at large substrate defects. Received: 2 May 1999 / Accepted: 17 August 1999 / Published online: 6 October 1999     

Gold nanoparticles modified GC electrodes: electrochemical behaviour dependence of different neurotransmitters and molecules of biological interest on the particles size and shape

Gold colloidal nanoparticles (AuNps), synthesized by gold chloride hydrate (HAuCl₄) chemical reduction were used to realize a modified glassy carbon electrode (GCE). Different shapes and sizes were observed, varying the molar ratio of HAuCl₄ and polyvinylpyrrolidone (PVP). The electrochemical behaviour of different neurotransmitters and molecules of biological interest (dopamine, caffeic acid, catechol, uric acid, epinephrine and serotonin) were investigated by cyclic voltammetry (CV) at the AuNps modified GCE and a dependence of the electrochemical response on the size and the shape of the particles was observed. The electrochemical responses were stable during time with a generic decreasing of the peak current after 10 days ranging from 5–10% for catechol, uric acid and serotonine to 10–15% for the other analytes. A study on the electrochemical interface of modified electrodes was also carried out by means of electrochemical impedance spectroscopy (EIS).     

VEGFR-2 targeted cellular delivery of doxorubicin by gold nanoparticles for potential antiangiogenic therapy

We report a novel gold nanobioconjugate system that achieves targeted delivery of the small molecule drug doxorubicin to endothelial cells using anti-VEGFR-2 antibody conjugated gold nanoparticles (GNPs). The reported nanobioconjugate system combines the inherent ability of GNPs to undergo high levels of derivatization with the precision of antibody recognition of a cell surface antigen. Transmission electron microscopy (TEM) and surface-enhanced Raman spectroscopy (SERS) confirmed intracellular presence of the GNPs. Using a VEGFR-2 expressing cell line and a cell line that is negative for the receptor, in combination with competition assay we established the cell specific targeted delivery of the nanobioconjugate. The nanobioconjugate system described here may have potential drug delivery applications for antiangiogenic cancer therapy.     

Micromotion compensation in a surface electrode trap by parametric excitation of trapped ions

We report a surface electrode trap with a relatively large trap depth (0.6–1.0?eV). The trap electrodes are formed by gold plating an alumina substrate. Calcium ions are trapped approximately 400?μm above the trap surface. We demonstrate micromotion compensation based on parametric resonance for surface electrode traps. Unlike the conventional method based on radio-frequency (rf)–photon correlation in which the wave vector of the laser beam must have a component parallel to the micromotion to be detected, the proposed method is independent of the laser propagation direction. This enables the micromotion component normal to the electrode surface to be detected without increasing the scattered light.     

Stripping voltammetry of Pb and Cu using a microcantilever electrode

Microfabricated silicon microcantilevers coated with gold on one side have been used as working electrode in a three-electrode electrochemical arrangement. In addition to electrochemical current, cantilever bending has been used as a signal for monitoring electrode reactions on the cantilever surface. The microcantilever bending was measured by an optical beam deflection method as the surface potential was scanned and electrochemical reactions occurred on the surface. The microcantilever bending due to differential surface stress was used to sense Pb and Cu using cyclic voltammetry (CV) and linear sweep stripping voltammetry (LSSV).     

Electrochemical and surface characterisation of gold nanoparticle decorated multi-walled carbon nanotubes

A novel type of gold nanoparticle/multi-walled carbon nanotube (AuNP/MWCNT) composite electrodes is presented. The electrochemical reduction of oxygen on these hybrid electrodes was studied using the rotating disk electrode (RDE) method. The AuNP/MWCNT nanocomposites were prepared by sputter deposition of gold in argon atmosphere on MWCNTs followed by heat-treatment of the catalyst at different temperatures. High-resolution scanning electron microscopy (HR-SEM), glancing incidence angle X-ray powder diffraction (GIXRD) and small-angle X-ray scattering (SAXS) techniques were employed to characterise the surface structure and morphology of catalyst materials. Au nanoparticles with diameter around 20 nm were dispersed at the tips and on the sidewalls of nanotubes. Electrochemical measurements were performed to demonstrate the electrocatalytic properties of the composite catalysts towards O₂ reduction in acid media. The successful preparation of AuNP/MWCNT nanocomposites by magnetron sputtering opens up the possibility of making an efficient dispersion of nanoparticles for electrocatalyst design.     

带电纳米颗粒与相分离的带电生物膜之间相互作用的分子模拟

纳米颗粒在纳米医药、细胞成像等领域有着非常广泛的应用,深入理解纳米颗粒与生物膜之间相互作用的微观机制是纳米颗粒合成与应用的重要基础.本文采用粗粒化分子动力学模拟的方法研究了带电配体包裹的金纳米颗粒与相分离的带电生物膜之间的相互作用.结果表明,通过改变金纳米颗粒表面的配体密度、配体带电种类和比例,以及膜内带电脂分子的种类,可以方便地调控纳米颗粒在膜表面或膜内停留的位置和状态.进一步从自由能的角度分析了带电纳米颗粒与带电生物膜之间相互作用的微观物理机制.本文对纳米粒子在纳米医药、细胞成像等领域的应用具有一定的理论参考意义.     

A novel fullerene lipoic acid derivative: Synthesis and preparation of self-assembled monolayers on gold

Synthesis and preparation of self-assembled monolayers of a novel fullerene lipoic acid derivative on gold are reported. The presence of densely packed SAMs was confirmed by ellipsometry and cyclic voltammetry. The electrochemical response of the modified electrode in organic media exhibits the first two redox peaks characteristic of the extended π-electron system of fullerene. C₆₀ surface coverage (1.4 × 10⁻¹⁰ mol cm⁻²) has been electrochemically determined by the redox process of the adsorbed fullerene moiety and by reductive desorption of the SAM in strong alkaline solution. Electrochemical data indicate that all four sulphur atoms are involved in the self-assembly process, providing an increase of SAM stability in comparison to mono or di-thiolated appended molecules. Visualisation of discrete fullerene molecules by scanning tunnelling microscopy supplied further evidence for gold modification and molecular distribution on the surface. Mixed monolayers of hexanethiol and fullerene derivatives in a proportion of 1:2 have been also studied with the purpose of controlling the amount and distribution of fullerene units on the gold surface.