Electrochemical biosensing based on noble metal nanoparticles

The interest in the fabrication of electrochemical biosensors with high sensitivity, selectivity and efficiency is rapidly growing. In recent years, noble metal nanoparticles (NMNPs), with extraordinary conductivity, large surface-to-volume ratio and biocompatibility, have been extensively employed for developing novel electrochemical sensing platforms and improving their performances. Through distinct surface modification strategies (e.g. self-assembly, layer-by-layer, hybridization and sol-gel technology), NMNPs provide well control over the microenvironment of biological molecules retaining their activity, and facilitate the electron transfer between the redox center of biomolecules and electrode surface. Moreover, NMNPs have been involved into biorecognition events (e.g. immunoreactions, DNA hybridization and ligand-receptor interactions) by conjugating with various biomolecules, chemical labels and other nanomaterials, achieving the signal transduction and amplification. The aim of this review is to summarize different strategies for NMNP-based signal amplification, as well as to provide a snapshot of recent advances in the design of electrochemical biosensing platforms, including enzyme/protein sensors focused on their direct electrochemistry on NMNP-modified electrode surface; immunosensors and gene sensors in which NMNPs not only participate into biorecognition, but also act as electroactive tags to enhance the signal output. In addition, NMNP alloy-based multifunctional electrochemical biosensors are briefly introduced in terms of their unique heterostructures and properties.

Electrodeposition of noble metal nanoparticles on carbon nanotubes

Noble metal nanoparticles can be electrodeposited on carbon nanotubes under potential control. The nanotube sidewalls serve both as the electrodeposition template and as the wire electrically connecting the deposited nanoparticles.     

Supported noble metal nanoparticles as photo/sono-catalysts for synthesis of chemicals and degradation of pollutants

This review summarizes the utilization of supported noble metal nanoparticles (such as Au/TiO2, Au/ZrO2, Ag/AgCl) as efficient photo/sono-catalysts for the selective synthesis of chemicals and degradation of environmental pollutants. Supported noble metal nanoparticles could efficiently catalyze the conversion of solar energy into chemical energy. Under UV/visible light irradiation, important chemical transformations such as the oxidation of alcohols to carbonyl compounds, the oxidation of thiol to disulfid...     

Intrinsic therapeutic applications of noble metal nanoparticles: past, present and future

Biomedical nanotechnology is an evolving field having enormous potential to positively impact the health care system. Important biomedical applications of nanotechnology that may have potential clinical applications include targeted drug delivery, detection/diagnosis and imaging. Basic understanding of how nanomaterials, the building blocks of nanotechnology, interact with the cells and their biological consequences are beginning to evolve. Noble metal nanoparticles such as gold, silver and platinum are particularly interesting due to their size and shape dependent unique optoelectronic properties. These noble metal nanoparticles, particularly of gold, have elicited a lot of interest for important biomedical applications because of their ease of synthesis, characterization and surface functionalization. Furthermore, recent investigations are demonstrating another promising application of these nanomaterials as self-therapeutics. To realize the potential promise of these unique inorganic nanomaterials for future clinical translation, it is of utmost importance to understand a few critical parameters; (i) how these nanomaterials interact with the cells at the molecular level; (ii) how their biodistribution and pharmacokinetics influenced by their surface and routes of administration; (iii) mechanism of their detoxification and clearance and (iv) their therapeutic efficacy in appropriate disease model. Thus in this critical review, we will discuss the various clinical applications of gold, silver and platinum nanoparticles with relevance to above parameters. We will also mention various routes of synthesis of these noble metal nanoparticles. However, before we discuss present research, we will also look into the past. We need to understand the discoveries made before us in order to further our knowledge and technological development (318 references).     

基于贵金属纳米颗粒生长的比色传感研究进展

近年来,作为颜色标记和信号发生器的贵金属纳米粒子由于其简单性和实用性而被广泛用于比色测定和传感的研究当中。本文综述了近十年基于贵金属纳米粒子生长的比色传感器策略和应用的最新进展,总结了基于贵金属纳米颗粒生长的单色及多色传感器的传感原理、分类及前沿应用,探索了其比色传感的信号产生、分类和放大机制。由于贵金属纳米粒子在不同尺寸、距离、形状、成分等基底上的生长会产生不同的LSPR共振峰以及显著的传感信号变化,我们详细讨论了贵金属纳米粒子在金纳米棒等晶种基底上生长的比色传感。最后,我们对目前该比色传感面临的挑战和未来前景进行了展望。     

Transition metal oxides in the electrocatalytic oxidation of methanol and ethanol on noble metal nanoparticles

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Organometallic approach to the synthesis and surface reactivity of noble metal nanoparticles

The use of organometallic precursors allows the synthesis in mild conditions of nanoparticles of uniform small size (1–3 nm) and of clean surface, which can be stabilized by polymers or ligands. These nano-objects display an interesting surface chemistry comparable to that of molecular species. This involves classical elementary steps of organometallic chemistry such as substitution and oxidative addition as well as ligand fluxionality. An overview of recent work in this field from our group will be presented including stabilization of metal nanoparticles by asymmetric ligands and preliminary catalytic attempts. To cite this article: K. Philippot, B. Chaudret, C. R. Chimie 6 (2003).     

A general approach to mesoporous metal oxide microspheres loaded with noble metal nanoparticles

Catalytic microspheres: A general approach is demonstrated for the facile preparation of mesoporous metal oxide microspheres loaded with noble metal nanoparticles (see TEM image in the picture). Among 18 oxide/noble metal catalysts, TiO(2)/0.1?mol?% Pd microspheres showed the highest turnover frequency in NaBH(4) reduction of 4-nitrophenol (see picture).     

Plasmonic photocatalysts: harvesting visible light with noble metal nanoparticles

The efforts to produce photocatalysts operating efficiently under visible light have led to a number of plasmonic photocatalysts, in which noble metal nanoparticles are deposited on the surface of polar semiconductor or insulator particles. In the metal-semiconductor composite photocatalysts, the noble metal nanoparticles act as a major component for harvesting visible light due to their surface plasmon resonance while the metal-semiconductor interface efficiently separates the photogenerated electrons and holes. In this article, we survey various plasmonic photocatalysts that have been prepared and characterized in recent years.     

Non-enzymatic electrochemical immunoassay using noble metal nanoparticles: a review

Electrochemical immunodetection has attracted considerable attention due to its high sensitivity, low cost and simplicity. Large efforts have recently made in order to design ultrasensitive assays. Noble metal nanoparticles (NM-NPs) offer advantages such as high conductivity and large surface-to-volume ratio. NM-NPs therefore are excellent candidates for developing electrochemical platforms for immunodetection and as signal tags. The use of biofunctionalized NM-NPs often results in amplified recognition via stronger loading of signal tags, and also in enhanced signal. This review (with 87 references) gives an overview on the current state in the use of NM-NPs in Non-enzymatic electrochemical immunosensing. We discuss the application of NM-NPs as electrode matrices and as electroactive labels (either as a carrier or as electrocatalytic labels), and compare the materials (mainly nanoparticles of gold, platinum, or of bimetallic materials) in terms of performance (for example by increasing sensitivity via label amplification or via high densities of capture molecules). A conclusion covers current challenges and gives an outlook. Rather than being exhaustive, the review focuses on representative examples that illustrate novel concepts and promising applications. NM-NPs based immunosensing opens a series of concepts for basic research and offers new tools for determination of trace amounts of protein-related analytes in environment and clinical applications.

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A general thermal process for the one-step preparation of well-stable noble metal nanoparticles

Heating sodium 3-thiophenemalonic acid-noble metal salt aqueous solution at 100°C, without the extra step of introducing other reducing agents and protective agents, results in the formation of well-stable noble metal that includes Au, Ag, Pt, or Pd nanoparticles. As-formed colloidal solutions were characterized by UV-vis absorption spectra and transmission electron microscopy and the nanoparticle formation process was also traced by time-dependent UV-vis absorption spectra. The text was submitted in English by the author.     

Template-free method to prepare polymer nanocapsules embedded with noble metal nanoparticles

In this paper, polymer nanocapsules embedded with noble metal nanoparticles and showing a good catalytic activity were prepared by a novel and convenient method.     

Optimization of profenofos organophosphorus pesticide degradation by zero-valent bimetallic nanoparticles using response surface methodology

This study synthesized bimetallic Fe/Ni nanoparticles and used them for catalytic degradation of profenofos, an organophosphorus pesticide. This novel bimetallic catalyst (Fe/Ni) was characterized by scanning electron microscopy (SEM), energy-dispersive X-ray analysis spectroscopy (EDAX) and X-ray diffraction (XRD). The bimetallic nano-catalyst was prepared at diameters of 20–50 nm and was shown to effectively degrade profenofos. A three-factor central composite design combined with response surface methodology was used to maximize profenofos removal using the bimetallic system. A quadratic model was built to predict degradation efficiency. ANOVA was used to determine the significance of the variables and interactions between them. Good correlation between the experimental and predicted values was confirmed by the high F-value (16.38), very low P-value (<0.0001), non-significant lack of fit, an appropriate coefficient of determination (R² = 0.936) and adequate precision (14.75). The highest removal rate attained was 94.51%.     

Ampholyte polystyrene spheres self-regulated deposition of noble metal nanoparticles for catalyst applications

The polystyrene (PS) spheres having dual functional groups were synthesized using emulsifier-free emulsion polymerization based on St/potassium persulfate/water system in the presence of V-50 as co-initiator. Fourier transform infrared (FTIR) confirms the presence of the sulfate and the amino groups on the surfaces of PS spheres. Transmission electron microscopy and X-ray photoelectron spectra revealed that the PS spheres were successfully deposited with catalytic palladium (Pd) or gold (Au) nanoparticles (NPs). The reduction of 4-nitroaniline to 4-phenylenediamine used as a model reaction was performed for catalysis studies and examined by ultraviolet. It was found that both Au and Pd PS dispersions show high catalytic activity. The Pd PS dispersion of 200 μl with only Pd content of 1.09 wt.% exhibits an excellent catalytic effect superior to the commercial Pd/C catalyst, i.e., less than 35 s taken for the completion of the reduction of 4-nitroaniline.     

Layer-by-layer coating of bacteria with noble metal nanoparticles for surface-enhanced Raman scattering

A simple layer-by-layer method to coat the bacterial cells with gold and silver nanoparticles (AuNPs and AgNPs) for the acquisition of surface-enhanced Raman scattering (SERS) spectra is reported. First, the bacteria cell wall is coated with poly (allylamine hydrochloride) (PAH), a positively charged polymer, and then with citrate reduced Au or AgNPs. In order to increase the stability of the coating, another layer of PAH is prepared on the surface. The SEM and AFM images indicate that the nanoparticles are in the form of both isolated and aggregated nanoparticles on the bacterial wall. The coating of bacterial cells with AgNPs or AuNPs not only serves for their preparation for SERS measurement but also helps to visualize the coated of bacterial cells under the ordinary white-light microscope objective due to efficient light-scattering properties of Au and AgNPs. A comparative study single versus aggregates of bacterial cells is also demonstrated for possible single bacterial detection with SERS. The two bacteria that differ in shape and cell wall biochemical structure, Escherichia coli and Staphylococcus cohnii, Gram-negative and -positive, respectively, are used as models. The preliminary results reveal that the approach could be used for single bacterial cell identification.     

“Small-particle limit” in the second harmonic generation from noble metal nanoparticles

In this paper, we have probed the origin of SHG in copper nanoparticles by polarization-resolved hyper-Rayleigh scattering (HRS). Results obtained with various sizes of copper nanoparticles at four different wavelengths covering the wavelength range 738–1907 nm reveal that the origin of second harmonic generation (SHG) in these particles is purely dipolar in nature as long as the size (d) of the particles remains smaller compared to the wavelength (λ) of light (“small-particle limit”). However, contribution of the higher order multipoles coupled with retardation effect becomes apparent with an increase in the d/λ ratio. We have identified the “small-particle limit” in the second harmonic generation from noble metal nanoparticles by evaluating the critical d/λ ratio at which the retardation effect sets in the noble metal nanoparticles. We have found that the second-order nonlinear optical property of copper nanoparticles closely resembles that of gold, but not that of silver.     

Understanding of thermal/thermo-oxidative degradation kinetics of polythiophene nanoparticles

The polythiophene nanoparticles (nano-PT) were prepared with average diameter of 20–35 nm. The nanostructurals of polythiophene were confirmed by TEM and SEM analyzes. The kinetics of the thermal degradation and thermal oxidative degradation of nano-PT were investigated by thermogravimetric analysis. Kissinger method, Flynn–Wall–Ozawa method, and advanced isoconversional method have been used to determine the activation energies of nano-PT degradation. The results showed that the thermal stability of nano-PT in pure N₂ is higher than that in air atmosphere. The analyzes of the solid-state processes mechanism of nano-PT by Criado et al. method showed: the thermal degradation process of nano-PT goes to a mechanism involving second-order (F ₂ mechanism); otherwise, the thermo-oxidative degradation process of nano-PT is corresponding to a phase boundary controlled reaction mechanism (R ₂ mechanism).     

Metal-assisted photochemical etching of gallium nitride using electrodeposited noble metal nanoparticles as catalysts

Porous gallium nitride (PGaN) layers were fabricated by metal-assisted photochemical etching (MaPCE) using electrodeposited platinum nanoparticles (PtNPs) or gold nanoparticles (AuNPs) as catalysts. After identification of a suitable negative potential and appropriate cyclic voltammetry (CV) conditions, high-density PtNPs or AuNPs were deposited onto a planar GaN substrate. Based on the concrete numerical values of energy levels, the generation, transfer and consumption of electrons and holes, and the assumption that localized galvanic cells are formed, an etching mechanism was proposed which may provide theoretical guidance for future work on etching of GaN and other semiconductor materials.