Correlation between catalytic activity and surface ligands of monolayer protected gold nanoparticles

Gold nanoparticles (GNPs) are known to be a very good catalyst. Also, the anchoring of GNPs with stabilizing ligands is essential for surface modification, tuning of size and shapes, and to prevent from aggregation in suspension. But the effect of ligand on the catalytic property of ligand-capped GNP is yet to be explored in detail. In this paper, we perform an in-depth study of effect of ligands on the catalytic activity of monolayer protected GNPs. For this study, a series of different ligand functionalized GNPs in suspension as well as functionalized GNPs' thin film on glass substrate are prepared and used as catalysts in two model reactions, viz. borohydride reduction of 4-nitrophenol and redox reaction between potassium ferricyanide and sodium thiosulfate. The functionalization of GNPs with any ligand reduces its virgin catalytic activity, no matter whether the GNPs are suspended or supported as thin film. An increase in alkyl chain length of alkanethiols and alkylamines ligands and their graft density to the surface of GNP reduces its catalytic activity. Interestingly, the capping of GNPs with 11-mercaptoundecanoic acid and 11-mercaptoundecanol ligands completely destroys its catalytic activity. The effect of anchoring group of ligand molecules on the catalytic activity of ligand-protected GNPs is also discussed.     

Recent advances in polymer protected gold nanoparticles: synthesis, properties and applications

The use of various functionalized polymers as stabilizers to design metal core-organic shell hybrid nanoparticle architectures has attracted increasing interest for different applications. The feature article reviews recent reports published from 2004 to the beginning of 2007 on the synthesis of polymer protected gold nanoparticles (AuNPs), and also comments their properties and applications.     

Chiral bisphosphine BINAP-stabilized gold and palladium nanoparticles with small size and their palladium nanoparticle-catalyzed asymmetric reaction

The reduction of tetrachloroaurate or potassium tetrachloropalladate with sodium borohydride in the presence of optically active 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl [BINAP] gave the chiral (S)- or (R)-BINAP-stabilized gold or palladium nanoparticles which showed the small core (1.7 nm for BINAP-Au and 2.0 nm for BINAP-Pd) with narrow size distribution and remarkably high stability. Asymmetric hydrosilylation of styrene with trichlorosilane in the presence of chiral BINAP-Pd nanoparticles afforded an optically active 1-phenyl-1-trichlorosilylethane which was converted into an optically active 1-phenylethanol (95% enantiomeric excess) by oxidative cleavage of the carbon-silicon bond.     

Hyperbranched polylysine: Synthesis,mechanism and preparation for NIR-absorbing gold nanoparticles

The hyperbranched polylysine fluoroborate was synthesized by NH₃BF₄-Lys NCA ROP in triethylamine at 15℃, during which the cyclic dimer mainly initiated ROP as the secondary initiating species. The hyperbranched polylysine can be used as a stabilizer to prepare the NIR-absorbing HPlys@Au NPs.     

Green preparation of hollow mesoporous silica nanosphere inside-loaded gold nanoparticles and the catalytic activity

In this work, an active nano-catalyst with gold nanoparticles loaded in hollow mesoporous silica nanospheres (HMSNs/Au) was prepared by a one-pot sol-gel method, in which gold ions were loaded in hollow mesoporous silica spheres followed by sodium alginate reduction. The characterization of the HMSNs/Au were determined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), N₂ adsorption–desorption isotherms (BET). The high catalytic activity of HMSNs/Au, denoted as apparent turn-over frequency (TOF), was detected by UV-Vis spectrophotometer for the catalytic reduction of 4-nitrophenol (74.5 h^?1) and 2-nitrophenol (108.7 h^?1) in the presence of sodium borohydride solution due to the small gold nanoparticles size and overall exposure of active sites. It is expected that this ecofriendly approach to prepare inorganic composited nanoparticles as high active catalysts based on hollow mesoporous materials was a promising platform for loading noble metal nanoparticles.     

Modelling the optical response of gold nanoparticles

This tutorial review presents an overview of theoretical methods for predicting and understanding the optical response of gold nanoparticles. A critical comparison is provided, assisting the reader in making a rational choice for each particular problem, while analytical models provide insights into the effects of retardation in large particles and non-locality in small particles. Far- and near-field spectra are discussed, and the relevance of the latter in surface-enhanced Raman spectroscopy and electron energy-loss spectroscopy is emphasized.     

Functionalized gold nanoparticles for sample preparation: A review

Sample preparation is a crucial step for the reliable and accurate analysis of both small molecule and biopolymers which often involves processes such as isolation, pre‐concentration, removal of interferences (purification), and pre‐processing (e.g., enzymatic digestion) of targets from a complex matrix. Gold nanoparticle (GNP)‐assisted sample preparation and pre‐concentration has been extensively applied in many analytical procedures in recent years due to the favorable and unique properties of GNPs such as size‐controlled synthesis, large surface‐to‐volume ratio, surface inertness, straightforward surface modification, easy separation requiring minimal manipulation of samples. This review article primarily focuses on applications of GNPs in sample preparation, in particular for bioaffinity capture and biocatalysis. In addition, their most common synthesis, surface modification and characterization methods are briefly summarized. Proper surface modification for GNPs designed in accordance to their target application directly influence their functionalities, e.g., extraction efficiencies, and catalytic efficiencies. Characterization of GNPs after synthesis and modification is worthwhile for monitoring and controlling the fabrication process to ensure proper quality and functionality. Parameters such as morphology, colloidal stability, and physical/chemical properties can be assessed by methods such as surface plasmon resonance, dynamic light scattering, ζ‐potential determinations, transmission electron microscopy, Taylor dispersion analysis, and resonant mass measurement, among others. The accurate determination of the surface coverage appears to be also mandatory for the quality control of functionality of the nanoparticles. Some promising applications of (functionalized) GNPs for bioanalysis and sample preparation are described herein.     

One pot synthesis of polymer protected gold nanoparticles and nanoprisms in glycerol

Uniform and stable polymer protected spherical gold nanoparticles were synthesized using glycerol as reducing agent. Further it was observed that the morphology of the particles varied from spherical to triangular prismatic gold nanoparticles when the reaction was changed from normal mode of reflux condition to microwave mode (MW) of heating. Further a brief mechanism relating the formation of prisms with the orientation of polymer and nucleation period has been discussed. Formation of triangular prismatic and spherical gold nanoparticles were characterised using UV–vis spectroscopy, transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis.     

Morphology-selective synthesis of polyhedral gold nanoparticles: what factors control the size and morphology of gold nanoparticles in a wet-chemical process

Polyhedral gold nanoparticles below 100 nm in size were fabricated by continuously delivered HAuCl(4) and PVP starting solutions into l-ascorbic acid aqueous solution in the presence of gold seeds, and under addition of sodium hydroxide (NaOH). By continuously delivered PVP and HAuCl(4) starting solutions in the presence of gold seed, the size and shape of polyhedral gold were achieved in relatively good uniformity (particle size distribution=65-95 nm). Morphological evolution was also attempted using different growth rates of crystal facets with increasing reaction temperature, and selective adsorption of PVP.     

Influence of particle size on the binding activity of proteins adsorbed onto gold nanoparticles

We used optical extinction spectroscopy to study the structure of proteins adsorbed onto gold nanoparticles of sizes 5-60 nm and their resulting biological binding activity. For these studies, proteins differing in size and shape, with well-characterized and specific interactions-rabbit immunoglobulin G (IgG), goat anti-rabbit IgG (anti-IgG), Staphylococcal protein A, streptavidin, and biotin-were used as model systems. Protein interaction with gold nanoparticles was probed by optical extinction measurements of localized surface plasmon resonance (LSPR) of the gold nanoparticles. Binding of the ligands in solution to protein molecules already immobilized on the surface of gold causes a small but detectable shift in the LSPR peak of the gold nanoparticles. This shift can be used to probe the binding activity of the adsorbed protein. Within the context of Mie theory calculations, the thickness of the adsorbed protein layer as well as its apparent refractive index is shown to depend on the size of the gold nanoparticle. The results suggest that proteins can adopt different orientations that depend on the size of the gold nanospheres. These different orientations, in turn, can result in different levels of biological activity. For example, we find that IgG adsorbed on spheres with diameter ≥20 nm does not bind to protein A. This study illustrates the principle that the size of nanoparticles can strongly influence the binding activity of adsorbed proteins. In addition to the importance of this in cases of direct exposure of proteins to nanoparticles, the results have implications for proteins adsorbed to materials with nanometer scale surface roughness.     

Gold nanoparticles in reverse micellar solutions: preparation,optical properties,and dimensional characteristics

Russian Chemical Bulletin - Gold nanoparticles (NPs) were synthesized via chemical (Chem) and radiation-chemical (RadChem) methods for the reduction of ions in reverse micellar solutions (RMS). The...     

Extinction coefficients of gold nanoparticles and their dimers. Dependence of optical factor on particle size

The generalized Mie theory has been employed to calculate extinction coefficients κ for isolated gold nanoparticles of different sizes (4–80 nm) and their dimers (κ₂) at the maximum of the short-wave plasmon resonance band. It has been found that the value of κ₂ essentially depends on both interparticle distance s and particle sizes R. According to the character of variations in the κ₂(s) dependence, three ranges of the distances are distinguished, i.e., large, intermediate, and small. In the first range, the κ₂ values slightly differ from doubled κ values. Nevertheless a tendency toward an increase in κ₂ is distinctly seen as the particles approach each other, and, within some range of s values and for particles with radii R < 15 nm, κ₂ is higher than 2κ. For dimers of larger particles, κ₂ < 2κ, with its value gradually decreasing with a reduction in the s value. The behavior changes when the particle sizes are of about 50 nm. In the range of small interparticle distances, κ₂ values slightly vary with the distance between the particles somewhat decreasing or oscillating with a small amplitude about some mean value. In this range, as the sizes of the gold particles grow, the extinction coefficients of dimers increasingly deviate from the sum of the extinction coefficients of the particles composing the dimers. For 20–80 nm nanoparticles, the size-dependence plotted for the extinction efficiency of dimers in logarithmic coordinates within the range of small interparticle distances is described by a straight line, the slope of which (1.036 ± 0.039) appears to be somewhat smaller than the slope of a corresponding line for individual gold particles (1.274 ± 0.014). The ratio between κ₂ and κ predetermines the character of variations in the optical factor as depending on the particle size and the interparticle distance and governs the behavior of the sol turbidity at the stage of nanoparticle dimerization.     

Interactions of Schiff-base ligands with gold nanoparticles: structural, optical and electrocatalytic studies

A study on optical and electrochemical properties resulting upon interaction of Schiff base ligands with gold nanoparticles is presented. The measurements of the optical absorption and fluorescence properties have provided important information about structure-properties dependence. We show that in function of the isomer structure and its attachment orientation with respect to the metal nanoparticle, their optical properties can be modulated. Nanoparticle assemblies mediated by 3,4-DHS were also obtained based on a control of the interparticle interactions and their electrocatalytic activity toward NADH oxidation was investigated.     

Silver nanodisks: size selection via centrifugation and optical properties

Silver nanodisks, having two different sizes, and spherical particles are synthesized by soft chemistry. By using centrifugation, nanodisks are mainly selected. The experimental absorption spectra of these nanodisks with different sizes are compared to those simulated using the discrete dipole approximation method. For small nanodisk sizes, the nanodisk shape is neglected and the simulated spectra closest to the experiments are obtained by assuming a spheroidal particle. Conversely, for larger nanodisks, the precise geometries represented by snip and aspect ratio are needed for good agreement between experiments and simulations.     

Evolution of size and shape in the colloidal crystallization of gold nanoparticles

The addition of dodecanethiol to a solution of oleylamine-stabilized gold nanoparticles in chloroform leads to aggregation of nanoparticles and formation of colloidal crystals. Based on results from dynamic light scattering and scanning electron microscopy we identify three different growth mechanisms: direct nanoparticle aggregation, cluster aggregation, and heterogeneous aggregation. These mechanisms produce amorphous, single-crystalline, polycrystalline, and core-shell type clusters. In the latter, gold nanoparticles encapsulate an impurity nucleus. All crystalline structures exhibit fcc or icosahedral packing and are terminated by (100) and (111) planes, which leads to truncated tetrahedral, octahedral, and icosahedral shapes. Importantly, most clusters in this system grow by aggregation of 60-80 nm structurally nonrigid clusters that form in the first 60 s of the experiment. The aggregation mechanism is discussed in terms of classical and other nucleation theories.     

Electrochemical and optical characterization of triarylamine functionalized gold nanoparticles

This paper describes the synthesis, structural analysis, and investigations of the optical and electrochemical properties of some gold nanoparticles (AuNPs) which consist of a triarylamine ligand shell attached to small gold cores (Au-Tara). The triarylamine chromophores were attached to small 4-bromobenzenethiol covered gold nanoparticles (ca. 2 nm in diameter) by Sonogashira reaction. This procedure yields triarylamine redox centers attached via π-conjugated bridging units of different length to the gold core. The AuNPs were analyzed with (1)H NMR spectroscopy, diffusion ordered NMR spectroscopy (DOSY), thermogravimetric analysis (TGA), and scanning transmission electron microscopy (STEM). Cyclic voltammetry (CV) technique was used to determine the composition of the redox active particles via the Randles-Sevcik equation. The optical and electrochemical properties of the Au-Tara nanoparticles and of their corresponding unbound ligands (Ref) were investigated with UV/vis/NIR absorption spectroscopy, Osteryoung square wave voltammetry (OSWV), and spectroelectrochemistry (SEC). These data show that the assembling of triarylamines in the vicinity of a gold nanoparticle can change the optical and electrochemical properties of the triarylamine redox chromophores depending on the kind and length of the bridging unit. This is due to gold core-chromophore and chromophore-chromophore interactions.     

Spherical ensembles of gold nanoparticles on silica: electrostatic and size effects

Core-shell ensembles of citrate-stabilized gold nanoparticles (20-80 nm) on submicron silica cores (330-550 nm) have been prepared by electrostatic self-assembly with shell packing densities as high as phi = 0.55.     

Structural organization of gold nanoparticles onto the ITO surface and its optical properties as a function of ensemble size

Self-assembly of citrate-stabilized gold nanoparticles (AuNPs) onto an optically transparent indium tin oxide (ITO) surface followed by neutralization of these particles using dodecanethiol as a surfactant have been demonstrated. X-ray photoelectron spectroscopic (XPS) studies revealed the partial removal of citrate ions from the immobilized AuNPs, which advances the dilution of electrostatic attraction between AuNPs and the APS (amino-terminated monolayer)-functionalized ITO surface. The resultant AuNPs restore their mobility to some extent and form small ensembles. Some of the immobilized AuNPs were completely removed from the surface due to neutralization, as confirmed by XPS studies. Interparticle distance and size of ensembles were manipulated by consecutive cycles of immobilization and neutralization of AuNPs. Controlled nanostructural fabrication progression, which leads to two-dimensional lateral growth of AuNPs, provides a method for systematically shifting the surface plasmon resonance band based on the increase in plasmon coupling among the closely placed AuNPs of an ensemble. The magnitude of shift increases with the size of ensemble. This manipulated chemical strategy offers a convenient and simple method to tune the optical properties of materials on a nanoscale.     

Double hydrophilic block copolymer monolayer protected hybrid gold nanoparticles and their shell cross-linking

This paper describes the syntheses of core/shell gold nanoparticles stabilized with a monolayer of double hydrophilic block copolymer and their stimuli responsiveness before and after shell cross-linking. The hybrid nanoparticles consist of gold core, cross-linkable poly(2-(dimethylamino)ethyl methacrylate) (PDMA) inner shell, and poly(ethylene oxide) (PEO) corona. First, diblock copolymer PEO-b-PDMA was prepared via the reversible addition-fragmentation chain transfer (RAFT) technique using a PEO-based macroRAFT agent. The dithioester end group of PEO-b-PDMA diblock copolymer was reduced to a thiol end group. The obtained PEO-b-PDMA-SH was then used to prepare diblock copolymer stabilized gold nanoparticles by the "grafting-to" approach. 1,2-Bis(2-iodoethoxy)ethane (BIEE) was utilized to selectively cross-link the PDMA residues in the inner shell. The stimuli responsiveness and colloidal stability of core/shell gold nanoparticles before and after shell cross-linking were characterized by laser light scattering (LLS), UV-vis transmittance, and transmission electron microscopy (TEM). At pH 9, the average hydrodynamic radius Rh of non-cross-linked hybrid gold nanoparticles starts to increase above 35 degrees C due to the lower critical solution temperature (LCST) phase behavior of the PDMA blocks in the inner shell. In contrast, Rh of the shell cross-linked gold nanoparticles were essentially independent of temperature. Core/shell gold nanoparticles before and after shell cross-linking exhibit reversible swelling on varying the solution pH. Compared to non-cross-linked core/shell gold nanoparticles, shell cross-linking of the hybrid gold nanoparticles leads to permanent core/shell nanostructures with much higher colloidal stability and physically isolates the gold core from the external environment.     

Effect of PVA surrounding medium on ZnSe nanoparticles: size, optical, and electrical properties

Polyvinyl alcohol (PVA) matrix was used to confine the particle size of ZnSe nanocrystallites as well as the variation of zinc (Zn) to selenium (Se) ion ratio which showed a remarkable decrease on the particle size as this ratio increased. The particle size decrease was monitored from the UV-vis absorption measurement as well as photoluminescence which suffered a blue shift with particle size decrease. The particle size was characterized with the aid of X-ray diffraction (XRD). The Raman spectra showed that, as the particle size increases, the peak position of the line centers (LO) mode were found to be red shifted from 239 to 234 cm(-1), accompanied by an increase in the full-width at half-maximum (FWHM). The electrical measurements and FT-IR spectra (overtone and normal) band vibration were used to study the effect of ZnSe NPs size on the PVA matrix.