Micro-PIXE study of gold archaeological objects

Several fragments of ancient gold objects coming from an Eneolithic hoard and from Pietroasa Cloca cu Puii de Aur (The Golden Brood Hen with Its Chickens) hoard, unearthed on Romanian territory, and two Romanian native gold nuggets samples were analyzed using micro-PIXE technique. The purpose of the study was to clarify the metal provenance. Trace and minor elements (Cu, Te, Sn, Pb, Ti, Cr, V, Mn, Ta) and platinum group elements (PGE) concentrations were estimated. The presence of inclusions (micrometer size areas of composition different from the surroundings) was investigated. We found Si and Ca inclusions on two Eneolithic samples, and Ta inclusions on two samples from Pietroasa hoard. The measurements suggested an alluvial origin of gold for the Eneolithic samples and give indications for the possible gold ore sources of Pietroasa hoard.     

Optimization of high-yield biological synthesis of single-crystalline gold nanoplates

In this work, single-crystalline gold nanoplates were obtained by reducing aqueous chloroauric acid solution with the extract of Sargassum sp. (brown seaweed) at room temperature. The gold nanoplates so obtained were characterized by UV-vis spectroscopy, X-ray diffraction, atomic force microscopy, and transmission electron microscopy. The formation of gold nanoplates was found to depend on a number of environmental factors, such as the time taken to age the seaweed extract, pH of the reaction medium, reaction temperature, reaction time, and initial reactant concentrations. The size of the gold nanoplates could be controlled to between 200 and 800 nm by manipulating the initial reactant concentrations. The yield of the flat gold nanocrystals relative to the total number of nanoparticles formed was as high as approximately 80-90%.     

A gold nanoparticle-based immunochromatographic assay: the influence of nanoparticulate size

Four different sized gold nanoparticles (14 nm, 16 nm, 35 nm and 38 nm) were prepared to conjugate an antibody for a gold nanoparticle-based immunochromatographic assay which has many applications in both basic research and clinical diagnosis. This study focuses on the conjugation efficiency of the antibody with different sized gold nanoparticles. The effect of factors such as pH value and concentration of antibody has been quantificationally discussed using spectra methods after adding 1 wt% NaCl which induced gold nanoparticle aggregation. It was found that different sized gold nanoparticles had different conjugation efficiencies under different pH values and concentrations of antibody. Among the four sized gold nanoparticles, the 16 nm gold nanoparticles have the minimum requirement for antibody concentrations to avoid aggregation comparing to other sized gold nanoparticles but are less sensitive for detecting the real sample compared to the 38 nm gold nanoparticles. Consequently, different sized gold nanoparticles should be labeled with antibody under optimal pH value and optimal concentrations of antibody. It will be helpful for the application of antibody-labeled gold nanoparticles in the fields of clinic diagnosis, environmental analysis and so on in future.     

Gold nanoparticle aggregation-based highly sensitive DNA detection using atomic force microscopy

The potential ability of atomic force microscopy (AFM) as a quantitative bioanalysis tool is demonstrated by using gold nanoparticles as a size enhancer in a DNA hybridization reaction. Two sets of probe DNA were functionalized on gold nanoparticles and sandwich hybridization occurred between two probe DNAs and target DNA, resulting in aggregation of the nanoparticles. At high concentrations of target DNA in the range from 100 nM to 10 μM, the aggregation of gold nanoparticles was determined by monitoring the color change with UV-vis spectroscopy. The absorption spectra broadened after the exposure of DNA–gold nanoparticles to target DNA and a new absorption band at wavelengths >600 nm was observed. However, no differences were observed in the absorption spectra of the gold nanoparticles at low concentrations of target DNA (10 pM to 10 nM) due to insufficient aggregation. AFM was used as a biosensing tool over this range of target DNA concentrations in order to monitor the aggregation of gold nanoparticles and to quantify the concentration of target DNA. Based on the AFM images, we successfully evaluated particle number and size at low concentrations of target DNA. The calibration curve obtained when mean particle aggregate diameter was plotted against concentration of target DNA showed good linearity over the range 10 pM to 10 nM, the working range for quantitative target DNA analysis. This AFM-based DNA detection technique was three orders of magnitude more sensitive than a DNA detection method based on UV-vis spectroscopy.     

Determination of gold in copper-bearing sulphide ores and metallurgical flotation products by atomic-absorption spectrometry

A method is described which is specific for the determination of gold in sulphide copper ores and concentrates. Direct decomposition with aqua regia was found to be incomplete. A carefully controlled roasting stage followed by treatment with hydrochloric acid and then aqua regia was effective for dissolving all the gold. The gold is extracted into 4-methylpentan-2-one (methyli-sobutylketone) then aspirated into a very lean air—acetylene flame and the gold determined by atomic-absorption spectrometry. No interferences were observed from large concentrations of copper, iron or nickel.     

Strategies for the analysis of coal by laser ablation inductively coupled plasma mass spectroscopy

A comparison between a laser-induced breakdown spectrometry-partial least squares (LIBS-PLS) method and methods based on some well-known techniques, such as induced-coupled plasma-atomic emission spectrometry (ICP-AES), flame atomic absorption spectrometry (FAAS), and atomic scanning microscopy (ASM) is presented in order to both validate the content of gold and silver in alloys to be used as solid standards and develop an alternative to the established methods for the hallmark of gold and silver in jewelry pieces. 17 alloys with gold concentrations ranging from 100 to 50% and 8 alloys with silver concentrations between 100 and 80% and variable concentrations of other metals usually present in jewels were used as solid standards in LIBS in order to develop a method as general as possible. The results obtained in the analysis of some alloys (9 for gold and 7 for silver) show that the proposed method is comparable with the official one.     

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.     

A versatile surfactant‐mediated synthetic route to gold/polyaniline derivative core/shell nanocomposites

This article describes a versatile two‐step method for gold/polyaniline derivative core/shell nanocomposites with the aid of nonionic surfactant F127. First, F127 and monomer were introduced to gold colloids followed by the addition of oxidant to initiate the polymerization of monomer to afford a conducting polymer shell around each gold nanoparticle. Experimental parameters, such as kinds and concentrations of surfactant and monomer, gold core size and shape, reaction time, were systematically investigated to disclose the underground mechanisms involved in the formation of gold/polymer core/shell nanocomposites. Furthermore, Fourier transform infrared, ultraviolet–visible, X‐ray diffraction, and X‐ray photoelectron spectroscopy techniques were used to characterize the gold/polymer core/shell nanocomposites. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3903–3912, 2010     

Formation process of two-dimensional networked gold nanowires by citrate reduction of AuCl4- and the shape stabilization

Gold nanowires with a two-dimensional (2-D) network structure were formed by citrate reduction of AuCl4- with a low concentration of citrate. The structure change during the growth processes was observed by transmission electron microscopy (TEM) and the variation in concentrations of gold species in the aqueous solution was monitored by UV-vis spectra and Inductively Coupled Argon Plasma Emission Spectrophotometer (ICAP). The formation of 2-D gold nanowires was induced by the small amount of reducing agent because the preliminary gold nanoparticles formed by reduction of AuCl4- were thermodynamically unstable in the aqueous solution due to the insufficient capping of citrate. One of the key points of nanowire formation is the preferential adsorption of AuCl4- instead of citrate ions on the surface of the preliminary gold particles, which results in an attracting force between gold nanoparticles. We propose a hit-to-stick-to-fusion model, in which gold nanoparticles adhere by the attraction force and stick together, causing selective deposition of reduced gold metallic species on the concave surface of the two sticking particles, followed by fusion into nanowires. Nanowires then connect with each other, forming a network structure. The evidence obtained from TEM observation of transformation from gold nanowires on a TEM grid to large nanoparticles by hydrogen gas reduction and time-resolved measurements of gold ions suggest that gold ions not only are crucial for the growth of gold nanowires but also play an important role in stabilizing the shape of gold nanowires during the formation process. This method for synthesizing 2-D gold nanowires is simple and relatively easy application to the synthesis of other metallic nanowires such as silver or platinum is expected.     

基于离心加速耗散作用的纳米金三角片高效分离方法研究

纳米金三角片由于制备和纯化困难,获得较纯、较好形貌的产物一直是个挑战。本文提出利用离心加速的耗散作用,采用十六烷基三甲基氯化铵(CTAC)作为絮凝剂,对纳米金三角片粗产物进行纯化,从而快速获得尺寸形貌均一且顶角保持尖锐的不同尺寸的三角形金纳米颗粒。通过紫外可见分光光度计对比了用不同浓度絮凝剂获得的胶体上清液与沉淀的颜色以及消光光谱,从而确定分离不同尺寸的金三角纳米颗粒所需的最佳絮凝剂浓度。通过透射电子显微镜(TEM)对比纯化前后颗粒形貌的变化,发现已有的静置纯化方法存在较大局限性,即耗时较长且对颗粒的形貌有明显影响;而辅助以离心加速的分离方法,不仅可实现对不同尺寸纳米金三角片的快速高效分离,且有效减小了纯化过程中纳米颗粒的尖端损失。特别是对小尺寸(边长小于50 nm)的三角纳米颗粒,经离心加速的耗散力诱导的凝聚作用分离所得的颗粒,其尖端仍能保持尖锐。此方法简便高效地实现了纳米金三角片的分离,并有望推广到其它成分、非球形、低对称性形貌的纳米颗粒的纯化。     

Influence of biomass and gold salt concentration on nanoparticle synthesis by the tropical marine yeast Yarrowia lipolytica NCIM 3589

Cell-associated gold nanoparticles and nanoplates were produced when varying number of Yarrowia lipolytica cells were incubated with different concentrations of chloroauric acid (HAuCl₄) at pH 4.5. With 10⁹ cells ml⁻¹ and 0.5 or 1.0 mM of the gold salt, the reaction mixtures developed a purple or golden red colour, respectively, and gold nanoparticles were synthesized. Nanoparticles of varying sizes were produced when 10¹⁰ cells ml⁻¹ were incubated with 0.5, 1.0 or 2.0 mM chloroauric acid salt. With 3.0, 4.0 or 5.0 mM HAuCl₄, nanoplates were also observed. With 10¹¹ cells ml⁻¹ nanoparticles were synthesized with almost all the gold salt concentrations. The cell-associated particles were released outside when nanoparticle-loaded cells were incubated at low temperature (20 °C) for 48 h. With increasing salt concentrations and a fixed number of cells, the size of the nanoparticles progressively increased. On the other hand, with increasing cell numbers and a constant gold salt concentration, the size of nanoparticles decreased. These results indicate that by varying the number of cells and the gold salt concentration, a variety of nanoparticles and nanoplates can be synthesized. Fourier transform infrared (FTIR) spectroscopy revealed the possible involvement of carboxyl, hydroxyl and amide groups on the cell surfaces in nanoparticle synthesis.     

Shape-controlled electrodeposition of gold nanostructures

A one-step, nontemplated, low-cost electrochemical method for the growth of gold nanostructures with different shapes is reported here. It is the first time that nanopyramidal, nanorod-like, and spherical gold nanostructures were fabricated on polycrystalline gold substrates through electrochemical overpotential deposition (OPD) by easily manipulating the deposited potentials and concentrations of HAuCl4. X-ray diffraction and electrochemical analyses revealed that the pyramidal structures are more extensively dominated by (111) facets in comparison with the other nanostructures. The nanopyramids, which have anisotropic structures, exhibited broad extinction over the visible region, most likely due to plasmon resonance. Oxygen reduction activity of a gold electrode with the pyramidal structures was lower than those of the electrodes with the other nanostructures since the activity at the gold (111) surface is lower than that at the (100) and (110) surfaces.     

浊点萃取-紫外可见分光光度法测定痕量金

建立了以四甲基联苯胺(TMB)为络合剂,非离子表面活性剂Triton-114为萃取剂的浊点萃取-紫外可见分光光度法测定痕量金的方法。考察了溶液的pH、络合剂和表面活性剂浓度、平衡温度和时间等条件对浊点萃取的影响。在最优条件下,该方法对金的富集倍数为12倍,线性范围为0～0.5μg/mL,检出限(3σ)为8.6ng/mL,相对标准偏差RSD为2.3%～3.6%(n=6),回收率在97%～102%之间。方法已用于工业废水中痕量金的测定。     

QCM 表面自组装胱氨酸1，3－桥连杯[4]芳烃膜用于识别气相丁胺

Two cystine-bearing 1,3-bridged calix[4]arenes were used as the coatings of the quartz crystal microbalance (QCM) with gold electrodes. The two calix[4]arene derivatives were self-assembled onto the gold electrode surface by the covalent attachment between the di-sulfur and gold. The compound of cystine-bearing bi-phenylalanine 1,3-bridged calix[4]arene (CPC) with longer alkyl chain had better self-assembled capacity onto the fresh surfaces of gold electrode than that of cystine-bearing 1,3-bridged calix[4]arene (CC) with comparably shorter alkyl chain.The modified QCM sensors were used to recognize the butylamine isomers in gas. The results showed that the QCM coated with both compounds had preferential affinity to n-butylamine, then i-butylamine, t-butylamine in the range of low concentrations, indicating that in the recognition process, the steric hindrance effect played an important role when forming complex with guest molecules. When the concentrations of the analytes were increased, the polarity and the magnetism of the butylamine became determinative factors. The reversibility was improved greatly and the equilibrium time was much shorter on the self-assembled film than on the film obtained by dropping coating.     

PVP 稳定的纳米 Au 溶胶对葡萄糖液相选择氧化的催化性能

 采用化学还原法制备了聚乙烯吡咯烷酮 (PVP) 稳定的纳米 Au 溶胶, 这种 Au 溶胶在葡萄糖空气氧化制葡萄糖酸反应中具有良好的催化性能. 考察了 PVP 加入量和氯金酸前驱液的浓度对反应活性的影响. 紫外-可见吸收光谱和透射电镜分析结果表明, 含有较小 Au 粒子的 Au 溶胶体系具有较高的催化活性. 当 PVP/Au 质量比为 40, 氯金酸浓度为100 μg/ml 时, 得到稳定的 Au 溶胶体系具有金粒子尺寸小、分布均匀的特点, 对葡萄糖氧化反应活性高, 葡萄糖的转化率达到 54.4%.     

Plasmonic-based colorimetric and spectroscopic discrimination of acetic and butyric acids produced by different types of Escherichia coli through the different assembly structures formation of gold nanoparticles

We present a plasmonic-based strategy for the colourimetric and spectroscopic differentiation of various organic acids produced by bacteria. The strategy is based on our discovery that particular concentrations of dl-lactic, acetic, and butyric acids induce different assembly structures, colours, and optical spectra of gold nanoparticles. We selected wild-type (K-12 W3110) and genetically-engineered (JHL61) Escherichia coli (E. coli) that are known to primarily produce acetic and butyric acid, respectively. Different assembly structures and optical properties of gold nanoparticles were observed when different organic acids, obtained after the removal of acid-producing bacteria, were mixed with gold nanoparticles. Moreover, at moderate cell concentrations of K-12 W3110 E. coli, which produce sufficient amounts of acetic acid to induce the assembly of gold nanoparticles, a direct estimate of the number of bacteria was possible based on time-course colour change observations of gold nanoparticle aqueous suspensions. The plasmonic-based colourimetric and spectroscopic methods described here may enable onsite testing for the identification of organic acids produced by bacteria and the estimation of bacterial numbers, which have applications in health and environmental sciences.     

An acetylcholinesterase enzyme electrode stabilized by an electrodeposited gold nanoparticle layer

Electrodeposition of colloidal gold nanoparticles onto a planar gold electrode was used to create a more favorable surface for the attachment of the enzyme acetylcholinesterase. Atomic force microscopy demonstrated that the gold nanoparticles roughened the surface consequently enhancing the interaction of the enzyme with the gold electrode. The enzyme-modified electrode sensor was utilized for the sensitive electrochemical detection of thiocholine at the gold surface after hydrolysis of acetylthiocholine by the immobilized enzyme. In the absence of the nanoparticle layer, the sensor response to acetylthiocholine was significantly reduced and the utility of the electrode was limited. The ability of the nanoparticle-based sensor to reliably measure concentrations of the organophosphate pesticide carbofuran at nM concentrations was demonstrated by monitoring the inhibition of the hydrolysis of acetylthiocholine. This relatively straightforward strategy is potentially valuable for the development of new devices for the sensitive detection of potentially dangerous and deadly neurotoxins.     

A high selective ion‐imprinted polymer grafted on a novel nanoporous material for efficient gold extraction

In this work, for the first time, an ion‐imprinted polymer was developed for selective extraction and determination of gold ions. To increase the sorbent efficiency, this polymer was coated on a novel nanoporous carbon‐based material, carbohydrate‐derived Max‐Planck Gesellschaft 1, which is also the first example of grafting imprinted polymer on nanoporous‐carbon material. These particles were applied successfully for preconcentration of ultratrace amount of gold ions, following determination by flame atomic absorption spectrometry. Some effective factors on the efficiency of gold ions extraction, such as concentration and volume of eluent, sample and eluent flow rates, and also effect of interfering ions especially palladium and platinum ions, were investigated. The LOD was determined to be 0.27 ng/mL. Furthermore, the precision of the method was calculated to be 2.14% under optimal conditions with recovery more than 97.3%. The technique was also used to determine the concentration of gold ions in mine stone samples with satisfactory results. The accuracy of this method was investigated by determination of gold ions concentrations in several reference materials with certified gold content.     

溶出伏安法同时测定矿山地下水中痕量砷铅

本文以电化学预处理的金电极为工作电极,采用线性扫描溶出伏安法实现了矿山地下水中痕量As3+、Pb2+的同时测定。研究了金电极的预处理方法、不同预富集时间和不同电解质对重金属离子测定的影响规律。研究发现,电化学预处理有利于金电极对重金属离子的响应,在最优实验条件下,As3+、Pb2+在电化学活化的金电极上分别于0.18V、-0.07V产生灵敏的溶出峰,峰高与其浓度线性相关,检测限分别可达到0.5!g/L、2!g/L。该方法操作简单、干扰小、线性范围宽、灵敏度高。     

Functionalization of Electrode Surfaces with Monolayers of Azocompounds and Gold Clusters

Properties of monolayers of azocrown compound self-assembled on gold substrates were studied using voltammetry and scanning tunneling microscopy. The surface concentrations of this compound in monolayers were determined from the area of the voltammetric reduction peaks. The area per one molecule estimated from voltammetry experiments is 0.65 nm². This value was comparable with the limiting molecular area of the compound in the Langmuir–Blodgett film at the air–water interface. We also observed the presence of gold clusters and other gold structures by STM when a gold electrode modified with azocrown compound was dipped into the tetrachloroaurate solution. Even better spectra of clusters were obtained following one voltammetric scan in the range 0.5 to ?0.6 V. After more cycles or if we condition the electrode at 0.4 V the clusters aggregate into wires.