Preparation of gold nanoislands on various functionalized polymer-modified glass and ITO for electrochemical characterization of monolayer assembly of alkanethiols

Nanometer dimension of citrate-capped gold nanoparticles can be firmly bound with various functionalized polymer-modified glass plate and indium tin oxide (ITO) substrates. Herein we report 3-aminopropyltriethoxysilane, polyvinyl pyridine, polyethylene imines, etc. as binding agents to modify these substrates to stabilize the charged colloidal gold nanoparticles through electrostatic stabilization of gold nanoparticles. When gold nanoparticles pretreated substrate are exposed into the seeding growth solution, the preadsorbed gold nanoparticles grow further and then form nanoislands of gold on glass and ITO substrates. The formation of nanoislands on microscope glass slide and ITO was monitored with UV-visible spectroscopy, cyclic voltammetry, and atomic force microscopy methods. The gold nanoislands and gold nanoparticles pretreated substrates can be used as platform to study the self-assembling behavior of long chain alkanethiols such as C₁₂SH, C₁₆SH, and C₁₈SH. The binding, coverage, and electron transfer characteristics of monolayer assembly on modified gold nanoisland and nanoparticles modified substrates are studied using electrochemical studies. The gold substrates can be prepared by this method, which is simple and reproducible and can be applied to various sensor and electrocatalytic applications.     

Oxygen plasma-treated gold nanoparticle-based field-effect devices as transducer structures for bio-chemical sensing

EIS (electrolyte-insulator-semiconductor) sensors based on the functionalization of uncoated gold nanoparticles supported on a Si/SiO₂ structure are presented. Oxygen plasma etching at moderate power (<200 W) provides a convenient and efficient way to remove organic capping agents from the gold nanoparticles without significant damage. Higher power intensities destroy the linkage between the SiO₂ and the gold nanoparticles, and some of the gold nanoparticles are removed from the surface. The flat-band potential shift, i.e. the pH dependence of the gold-coated EIS sensors is similar (33 mV/pH) to the uncoated EIS pH-sensor. Lead, penicillin and glucose sensors were prepared by immobilization of β-cyclodextrin, penicillinase and glucose oxidase by various immobilization techniques.

     

Cucurbit[7]uril as a Tool in the Green Synthesis of Gold Nanoparticles

A simple, green, one‐pot synthesis of gold nanoparticles was achieved through the reaction of an aqueous mixture of potassium tetrachloroaurate(III) and the macrocycle cucurbit[7]uril in the presence of sodium hydroxide at room temperature without introducing any kind of traditional reducing agents and/or external energy. The as‐prepared gold nanoparticles showed catalytic activity for the reduction reaction of 4‐nitrophenol in the presence of NaBH₄, which has been established by visual inspection and UV/Vis spectroscopy. This report is the first for the preparation of gold nanoparticles using cucurbit[7]uril in aqueous media through chemical reduction without employing conventional reducing agents and/or external energy.     

Dipyrromethane as a new organic reagent for the synthesis of gold nanoparticles: preparation and application

Condensation reaction of several ketones with pyrrole in the presence of ferric hydrogen sulfate as a green homogenous acidic catalyst furnished the corresponding pure dipyrromethanes in good yields. Gold nanoparticles were produced through reduction of HAuCl₄ with substituted dipyrromethanes as new reducing agents at room temperature with the exclusion of any capping agent or surfactant. Gold nanoparticles were characterized by transmission electron microscopy, scanning electron microscopy, XRD and UV–visible absorption spectroscopic measurements. It is proposed that in situ formed oxidative products of dipyrromethane, such as polydipyrromethane could serve effectively as a capping agent to preferably adsorb the {111} facets of gold crystals during the reduction process, which leads to the formation of gold nanoparticles.     

Block copolymers in the synthesis of gold nanoparticles. Two new approaches: Copolymer aggregates as reductants and stabilizers and simultaneous formation of copolymer aggregates and gold nanoparticles

In this article, innovative applications of amphiphilic triblock and pentablock copolymers in the synthesis of gold nanoparticles are reported. The synthesis of gold nanoparticles is performed using two methods. In the first method, micellar aggregates of block copolymers and AuCl₄^? ions directly react in water; the nanoparticles obtained by this method are variable in size and are associated with copolymer aggregates. In the second method, two processes take place simultaneously: the aggregation of block copolymers and the reduction of Au (III) by the copolymers to form nanoparticles. In contrast with the first method, in this case, the nanoparticles obtained are located inside the copolymer aggregates. In both methods of synthesis, the block copolymers act simultaneously as reducing and stabilizing agents. To understand the role of copolymer aggregates in the synthesis of nanoparticles, molecular simulation methods are used. The gold nanoparticles, copolymer aggregates, and nanocomposite systems are characterized using transmission electron microscopy and dynamic light scattering. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3069–3079     

Fabrication and Characterization of Iron (II,III) on Positively Charged Gold Nanoparticles with Application for Magnetically Recoverable Catalysis

An aqueous dispersion was prepared by attaching positively charged gold nanoparticles to the surface of poly-sodium-p-styrenesulfonate-modified Fe₃O₄ nanoparticles. The Fe₃O₄@positively charged gold nanoparticles offer high monodispersion, stability against aggregation, and high magnetization with uniform size. The Fe₃O₄@positively charged gold nanoparticles were efficient and recyclable catalysts due to the formation of a positively charged gold layer on the surface of Fe₃O₄ nanoparticles and were stable in aqueous solution for over forty-eight hours and hence may have a broad range of applications.     

Theoretical studies of magnetic interaction in organic π-radical and gold cluster hybrid systems

Nanoscale magnetic material is becoming an important topic in nanoscience and magnetism. Especially, gold nanoparticles chemisorbed by alkanethiols have drawn much attention due to the size effect on their electronic structure. However, magnetic interaction of gold nanoparticles derivatized by magnetically active ligands has not been investigated in detail. In order to elucidate the magnetic interaction in gold nanoparticles chemisorbed by alkanethiol systems, small gold cluster, such as Au₃ and Au₁₃, and π-radical hybrid model systems were examined using the hybrid DFT method.     

One‐Step Synthesis and Size Control of Dendrimer‐Protected Gold Nanoparticles: A Heat‐Treatment‐Based Strategy

Dendrimer‐protected gold nanoparticles have been facilely obtained by heating an aqueous solution containing third‐generation poly(propyleneimine) dendrimers and HAuCl₄ without the additional step of introducing other reducing agents. Transmission electron microscopy (TEM) and UV‐vis data indicate the size, the nucleation, and growth kinetics of gold nanoparticles thus formed, which can be tuned by changing the initial molar ratio of dendrimer to gold.

The formation of dendrimer–gold nanoparticles by the heat treatment of an aqueous solution containing third‐generation poly(propyleneimine) dendrimers and HAuCl₄.     

Synthesis of gold nanoparticles in sol–gel glass porogens containing [bmim][BF4] ionic liquid

The [bmim][BF₄] ionic liquid effect on gold nanoparticles formation in silica sol–gel materials is studied in order to produce gel-derived glasses with optical properties. The characteristic red color from gold nanoparticles is observed for transparent glass monoliths obtained sintering, between 365 and 425 °C, a silica sol–gel precursor containing HAuCl₄·3H₂O and [bmim][BF₄], under normal atmospheric conditions. The effect of sintering the ionogel at different temperatures (T_sint) or times (t_sint) on the optical properties, shape, size, and distribution of gold nanoparticles is discussed. Presence of the gold particles is observed using transmission electron microscopy images followed by energy dispersive X-ray spectroscopy analysis. The thermal decomposition of [bmim][BF₄] in the ionogel is investigate using calorimetric and spectroscopic techniques, and by analysis of volatile compounds released by the sol–gel material during sintering. With these results a mechanism for the formation of the gold nanoparticles is proposed, where a first ionic liquid degradation step provides the reductive environment that enables the gold nanoparticles production at the range of temperatures between 350 and 425 °C. Upon sintering the synthesized materials the ionic liquid acts as a sacrificial additive and the ionic liquid thermal decomposition products enables the formation of gold nanoparticles in the sol–gel matrix.     

Effect of gold nanoparticles on an aerosil surface on the fluorescence and Raman spectra of adsorbed tryptophan

We discuss the fluorescence and Raman spectra of the amino acid tryptophan (Trp) in the presence of gold nanoparticles in solution and on the surface of highly dispersed silica (aerosil) containing gold nanoparticles (Au-SiO₂). The fluorescence of Trp is efficiently quenched in the presence of gold nanoparticles both in solution and on the SiO₂ surface. The fluorescence and excitation spectra contain bands for molecular Trp and a charge transfer complex between Trp and the nanoparticles. In the Raman spectra of Trp with gold nanoparticles, considerably enhanced intense vibrations appear for the carboxyl and amino groups and also for the benzene and pyrrole rings. The effect of gold nanoparticles on the Raman spectra of Trp in a heterogeneous system is considerably weakened due to strong light scattering by the dispersed silica.     

Photochemical synthesis of gold nanoparticles in N,N′-dimethylformamide via thiourea-derivatized polyoxometalate

In the present work, we report the photochemical synthesis of gold nanoparticles in N,N′-dimethylformamide by addition of a photocatalyst like thiourea-modified polyoxometalate (γ-SiW₁₂O₄₀). The polyoxometalate behaves as an electron relay. Reduction of the polyoxometalate takes place under UV irradiation followed by a transfer of electrons to the gold ions, leading to the formation of gold nanoparticles. The formation of the gold particles was monitored with time by UV–Vis spectrophotometry. The polyoxometalate also acts as a stabilizing agent and helps in controlling the size of the nanoparticles. The shape and size distribution was obtained from transmission electron microscopy studies. Spherical and monodisperse gold nanoparticles of ~10 nm size were obtained.     

Flow field-flow fractionation: a versatile approach for size characterization of α-tocopherol-induced enlargement of gold nanoparticles

Flow field-flow fractionation (FlFFF) was used for size characterization of gold nanoparticles. The measured particle sizes obtained from FlFFF for the commercial 10 nm gold nanoparticle standard and the gold nanoparticles synthesized in the laboratory were in good agreement with those measured by transmission electron microscopy (TEM). Further, the capability of α-tocopherol to induce enlargement of gold nanoparticles by catalysis of the reduction of AuCl₄⁻ by citrate was observed by monitoring the changes in particle size of gold nanoparticles using FlFFF. The effects of α-tocopherol and incubation time on enlargement of the gold nanoparticles were examined. Higher concentrations of α-tocopherol resulted in larger nanoparticles. At fixed α-tocopherol concentration, larger nanoparticles were formed at longer incubation times.     

Preparation and Characterization of Heparin‐Stabilized Gold Nanoparticles

A simple method for preparing gold nanoparticles in aqueous solution has been developed by using glycosaminoglycan‐heparin as reducing and stabilizing agent and HAuCl₄ as precursor. The obtained gold nanoparticles were characterized by UV‐vis spectroscopy, resonance light scattering spectroscopy (RLS), transmission electron microscopy (TEM) and electrophoresis technology. The influence of reactant concentration for the preparation of gold nanoparticles was investigated. The results indicated that the gold nanoparticles carried negative charges in the aqueous solution and the size and shape of the gold nanoparticles could be controlled by changing the concentration of the heparin. Moreover, the gold nanoparticles obtained with relatively high concentration of heparin were very stable and had relative narrow size distribution.     

An approach for the surface functionalized gold nanoparticles with pH-responsive polymer by combination of RAFT and click chemistry

In this report, we demonstrated a novel efficient post-modification route for preparation of smart hybrid gold nanoparticles with poly(4-vinylpyridine) (P4VP) based on RAFT and click chemistry. A new azide terminated ligand was first synthesized to modify gold nanoparticles by ligand exchange reaction, and then click reaction was used to graft alkyne terminated P4VP which was prepared by RAFT onto the surface of gold nanoparticles. The functionalized hybrid gold nanoparticles were characterized by TEM, FTIR, and XPS etc. The results indicated that the P4VP was successfully grafted onto the surface of gold nanoparticles by click reaction. The surface grafting density was calculated to be about 6 chains/nm²_. In addition, the hybrid gold nanoparticles showed a pH responsive phenomenon as the pH value changed around 5.     

Biosynthesis of Gold Nanoparticles by Streptomyces sp. ERI-3 Supernatant and Process Optimization for Enhanced Production

In this study, we present a simple and eco-friendly method for extracellular biosynthesis of gold nanoparticles by Streptomyces sp. ERI-3 cell-free supernatant. The research was also aimed to evaluate the effects of different reaction parameters including incubation temperature, reaction time, HAuCl₄ concentration and pH on gold nanoparticles production. The UV?CVis spectroscopy was used to monitor the formation of gold nanoparticles. The synthesized gold nanoparticles were characterized with XRD, TEM, and SEM. The average particle size ranged from 10 to 30?nm with spherical shape at optimum conditions.     

Deposit of UV- or γ-synthesized gold nanoparticles on TiO2 powder using lipid-based multilamellar vesicles

This article describes a general method for the deposition of gold nanoparticles onto solid support based on the use of multilamellar vesicles (MLVs). Gold nanoparticles (nps) synthesized within lipid-based MLVs by UV- or γ-irradiation were deposited onto TiO₂ powder support. The organic phase from MLVs was removed by calcination leading to high dispersion of naked Au nanoparticles. The resulting particles were investigated using spectrometry, electron microscopy and XPS. The gold nanoparticles were stable and well-separated on the titania surface. It was found that the metal nanoparticles produced by radiolysis have smaller average size and narrower size distribution than those synthesized by photochemical route. After calcinations, the particles tended to enlarge to reach c.a. 18 nm. The gold loading on the titania support could be controlled by changing the gold salt concentration and the MLV-to-TiO₂ weight ratio; values of Au-to-Ti ratio up to 44 % could be obtained.     

Theoretical studies of magnetic interaction of organic π-radicals on gold cluster surface

Nanoscale magnetic material is the important topic in nanoscience and magnetism. Especially, gold nanoparticles chemisorbed by alkanethiols are one of the promising material for these purposes. However, magnetic interaction of magnetically active ligands grafted onto the surface of gold nanoparticles has not been investigated in detail. In order to elucidate the magnetic interaction in gold nanoparticles chemisorbed by alkanethiol systems, small slab gold cluster, such as Au₁₀, and π-radical hybrid model systems were examined using the hybrid DFT method.     

Regioselective Bridging Calix[6]arenes: Synthesis and X-ray Structure of Trisbridged Calix[6]arene

The preparation and characterization of gold nanoparticles (～6 nm in diameter) modified with mono-6-thio-β-cyclodextrin (II) is described. The resulting monolayer-protected gold nanoparticles are water-soluble and more stable. The concentration of II plays a crucial role for the distribution of the modified nanoparticles. When the ratio of concentration of II to HAuCl₄,[II]/[HAuCl₄] ≥ 0.93, a stable gold nanoparticle with uniform distribution and diameter of 6.0 ± 0.9 nm will be obtained. The recognition of modified gold nanoparticles to organic guest molecule is researched. The modified gold nanoparticles can make the electrochemical reduction current of nitrobenzene decrease and can be self-assembled in three-dimensional to form spherical clusters with ligand of methylene green.     

纳米金的绿色合成与CTAB对金纳米聚集体的解聚集作用

室温下利用鞣酸(TA)既作还原剂又作保护剂,通过绿色还原方法制备了鞣酸包裹的金纳米粒子,并通过紫外可见光谱(UV-Vis)、透射电镜(TEM)、X射线衍射(XRD)、红外光谱(FTIR)等分别进行了表征和分析。结果表明,随着nTA/nHAuCl4比率的增加,紫外可见光谱显示鞣酸稳定的金溶胶最大吸收波长明显增大且吸收带变宽,而最大吸光率逐渐减小。TEM观察证实增加鞣酸用量会导致溶胶体系中花状金纳米聚集体的形成。实验发现,阳离子型表面活性剂十六烷基三甲基溴化铵(CTAB)对鞣酸保护的金纳米聚集体具有强烈的解聚集作用,在剧烈搅拌的条件下CTAB能使金纳米聚集体成功解聚为单分散状态的金纳米粒子,提高体系温度可明显促进CTAB对金纳米聚集体的解聚集作用。     

大肠杆菌为模板制备Au@TiO_2催化剂及其CO氧化反应活性

许多微生物对金属离子有较强的吸附还原能力.本文利用大肠杆菌(DH5α)对金属离子较强的吸附与还原能力制备了Au@DH5α,再利用大肠杆菌的水分来水解钛酸四丁酯,得到Au@DH5α-Ti(OH)4样品,焙烧去除大肠杆菌后得到氧化钛包裹的纳米金粒子催化剂Au@TiO2.以N2吸附,X射线衍射(XRD),紫外-可见漫反射光谱(UV-VisDRS),热重-差热分析(TG-DTA),透射电镜(TEM)对所得材料进行表征.结果表明:该催化剂具有与大肠杆菌类似的杆状结构,以大肠杆菌为生物模板生成的氧化钛孔道结构在一定程度上抑制了金粒子的聚集长大.随菌体用量的增加,金粒子减小,等离子共振吸收发生紫移,催化剂有较大的比表面积,但催化剂中积炭量也会增加.将该催化剂用于CO氧化反应,发现当菌体用量为100或150mL时,制得的金催化剂可在80℃下将CO完全氧化为CO2.