Light Absorption by the Clusters of Colloidal Gold and Silver Particles Formed During Slow and Fast Aggregation

Spectra of absorption (400–800 nm) by the aggregates of colloidal gold (5, 15, and 30 nm in diameter) and silver (20 nm in diameter) particles were studied experimentally and theoretically. It was revealed that, during fast aggregation corresponding to the diffusion-limited cluster aggregation (DLCA), the pattern of spectra is dependent on the size of primary particles. Spectra with the additional absorption maximum in the red region are observed for 15 and 30 nm gold and 20 nm silver particles, while the absorption spectrum for 5 nm particles is characterized by only one maximum shifted to the red region. The slow aggregation resulted in a decrease in plasmon absorption peak with no marked shift to the red region and to the broadening of long-wave absorption wing. From data on electron microscopy, typical branched DLCA-clusters were formed during fast aggregation, whereas small compact aggregates and a noticeable number of single particles were observed in a system during slow aggregation. The computer model of the diffusion-limited cluster-cluster aggregation was used to explain these results. Optical properties of aggregates were calculated using coupled dipole method (CDM or DDA) and the exact method of a multipole expansion. Corrections for the size effect were introduced into the bulk optical constants of metals for nanosized particles. It was shown that a modified version of DDA (Markel et al.,Phys. Rev. B, 1996, vol. 53, no. 5, p. 2425) allows us to explain the pattern of experimental spectra of DLCA-aggregates and their dependence on a monomer size. The exact method was applied to calculate the extinction cross sections of metallic aggregates demonstrating strong electrodynamic interaction between particles. The number of higher multipoles that are required to adequately describe this interaction is much larger than the number of terms of an ordinary Mie series and is the main obstacle to the exact calculation of the spectra of metallic aggregates with a large number of particles.     

胶体金在DNA分子识别中的应用——胶体金对罗丹明B与单双链DNA识别作用的影响

通过研究罗丹明B与单双链DNA作用过程中，胶体金加入前后的紫外可见吸收光谱的变化，发现在胶体金加入的前后，罗丹明B均以沟槽方式与单双链DNA相作用；胶体金的加入可以较大程度地增大化合物与DNA之间的相互作用．     

Colloidal Synthesis of Gold Semishells

This work describes a novel and scalable colloid chemistry strategy to fabricate gold semishells based on the selective growth of gold on Janus silica particles (500 nm in diameter) partly functionalized with amino groups. The modulation of the geometry of the Janus silica particles allows us to tune the final morphology of the gold semishells. This method also provides a route to fabricating hollow gold semishells through etching of the silica cores with hydrofluoric acid. The optical properties were characterized by visible near-infrared (vis-NIR) spectroscopy and compared with simulations performed using the boundary element method (BEM). These revealed that the main optical features are located beyond the NIR region because of the large core size.     

Fulminating Gold and Silver

This Essay deals with the fascinating and highly explosive compounds fulminating gold and fulminating silver, which are easily made by treatment of gold dissolved in aqua regia with ammonia, and by reaction of silver oxide or silver salts with ammonia, respectively. Fulminating gold in particular captivated the alchemists in the 16th to 18th centuries. Numerous preparations were described, as well as numerous attempts to make volatile, sublimable or distillable gold, and to use the products so obtained (which were most likely gold chlorides) to make the sought‐after tincture, which would “heal” the “impure” metals and transform them into gold, and equally be a panacea to cure all human illnesses.     

纳米银、金溶胶的电化学合成及其基本胶体性质——物理化学综合实验设计

电化学和胶体体系基础理论是大学本科物理化学学习的重要内容。通过综合化学实验设计,以直接电化学还原方法制备纳米银、金溶胶,利用紫外-可见光谱分析溶胶粒子的特征吸收光谱,并运用循环伏安法探讨表面活性剂的稳定作用和纳米金属溶胶的形成机理,从而提高学生的基础知识综合运用能力与综合实验技能,适合在大学化学及其相关专业的综合化学实验中推广。     

Modification of Synthetic Latexes with Colloidal Silver

Butadiene-styrene and acrylate latexes were studied as matrices for preparing colloidal silver. Colloidal-chemical and strength properties of the modified latexes and Primal E1950 latex films were studied. The heat resistance of these materials was determined.     

稳定分散的纳米银溶胶的制备及其表征

Stable aqueous dispersive colloidal Ag nanoparticles were prepared by reducing silver nitrate with sodium borohydride in the presence of 3-mercaptopropionic acid. The formation process of the Ag nanoparticles was investigated by UV-Visible spectroscopy and transmission electron microscopy. The results show that the spherical and rodlike particles and aggregates are formed in the initial stage of the reaction， then the rodlike particles and aggregates are gradually decomposed into small spherical particles， and the final obtained Ag nanoparticles with an average size of 8 nm are in uniform shapes and narrow size distribution， and the colloid remains stable for more than one month， which makes it convenient for use in practice. The presence of capping agent plays an extra role over nanoparticles stabilization and morphology. The presence of capping agent on the surface of Ag nanoparticle is confirmed by the X-ray photoelectron spectroscopy. It is found that Ag nanoparticles are negatively charged in alkaline condition， whereas they are positively charged in acid condition. Electrosteric effect is responsible for their long-term stability.     

免疫胶体金技术的应用与展望

免疫胶体金技术是一种新型固相标记免疫检测技术,因其独特的性质在许多领域得到广泛应用和快速发展。简述了免疫胶体金技术在电镜、光镜快速检测诊断中的发展以及在生物医学、免疫组织化学和细胞生物学等领域的研究和应用。未来免疫胶体金技术在提高胶体金制备质量的同时将实现定量和多元化检测。     

The Role of Colloidal Stability in the Formation of Gold Sols

The stability of gold sols, formed by the reduction of AuCl^-₄ with trisodium citrate, was examined as a function of reaction time using optical spectroscopy and direct force measurements performed with an atomic force microscope (AFM). The competitive adsorption of the ions and the effects of each species on the dispersion forces for the sol are examined. Analysis of the data suggests that the AuCl^-₄ is adsorbed preferentially at the gold/water interface but, due to its lower charge density, is not as efficient a dispersion agent as the trivalent citrate anion. The use of raw force data from the AFM to attain a qualitative understanding of colloidal phenomena is also demonstrated with this study.     

胶质液体泡沫的微观结构研究

采用冷冻蚀刻电子显微镜技术(FF-TEM)、小角X射线散射(SAXS)、偏光显微镜以及差示扫描量热分析(DSC)等手段对组成为十二烷基醇聚氧乙烯(3)醚(AEO-3)/正癸烷/十二烷基硫酸钠(SDS)或Tween 80/水的胶质液体泡沫(CLA)体系的微观结构进行了系统分析. 分析结果表明, CLA是由微米级的油相颗粒(富油相)和包围着它的外层水相液膜(富水相)组成, 且在富油相和富水相区内分别有诸如反胶束和胶束或O/W微乳液等超分子聚集体结构存在. 通过对不同组成和不同相体积比(PVR)的CLA之间, 以及与高内相普通乳状液(HIPRE)在粒径大小、组成、制备方法、结构特征、稳定性等方面的比较, 发现CLA与HIPRE具有相似的结构轮廓. 这一结论在一定程度上支持了Princen等有关CLA结构与本质的论点.     

Spectral Extinction of Colloidal Gold and Its Biospecific Conjugates

We have prepared gold sols with mean particle diametersd_min the range 4 to 50 nm and measured their extinction spectra and size dependences of the extinction peak position λ_maxand valueE_max. The measured increasing function λ_max(d_m) displays a pronounced bend near the particle diameterd_m∼ 10 nm, where the value of λ_maxsharply decreases with reduction in the particle size. To explain these findings, the extinction spectra of sols with the particle size and axial ratio polydispersity are calculated using Mie's theory, the T-matrix method, and various experimental sets of the bulk gold optical constants modified with regard to size-limiting effects. It is shown that the measured λ_max(d_m) andE_max(d_m) dependences are inconsistent with calculations based on Mie's theory and the bulk gold optical constants. The most generalized model including the size dependence of the imaginary part of the dielectric permeability and the size and shape polydispersity gives good agreement with experimental extinction spectra for 5-, 10-, 24-, and 40-nm sols, as well as with the measured functions λ_max(d_m) andE_max(d_m). Based on electron-microscopic and spectral data, calibration curves are obtained for efficient spectrophotometric control over the particle size and for estimation of the amount of restorer essential for the preparation of particles of a given size. A simplest two-layer spherical model is employed to elucidate the basic changes in sol spectra after conjugation with specific biomacromolecules and to draw some conclusions about the conjugate shell structure.     

Colloidal Gold Nanoparticles Protected by Cationic Polyelectrolytes

Abstract

Several stable gold colloids were prepared by the in-situ reduction of hydrogen tetrachloroaurate (HAuCl₄) in the presence of various cationic polyelectrolytes. Several types of such polyelectrolytes were investigated for their ability to stabilize gold colloids, and UV – VIS spectroscopy was used to follow the in-situ reductions and to further characterize the colloids. The particle sizes and size distributions were determined by transmission electron microscopy (TEM). TEM micrographs and UV-VIS spectra were also used to characterize the stability of the colloids after storage for nine months in air at room temperature. Colloids protected by the cationic polyelectrolytes with ammonium side-groups along a hydrophobic polymer backbone frequently exhibited very good stability.     

银溶胶体系表面增强拉曼散射光谱的溶剂效应

研究了银溶胶体系表面增强拉曼散射光谱的溶剂效应,发现在不同的溶剂中,银溶胶的聚集状态不同,当胶粒带电荷时,溶剂还能影响分子在胶粒表面的吸附,溶剂通过改变胶粒的聚集状态及分子在胶粒上的吸附这两个因素影响银溶胶体系的SERS光谱。     

Gold and Silver Complexes with Thiotriazoles and Thiotetrazoles

Abstract

The potential of thiotriazoles and thiotetrazoles in coordination chemistry towards gold and silver derivatives still remains largely unfulfilled. These substrates can function as ideal S,N donor ligands and form covalent or coordinative bonds with gold and silver. Relying on this, a comprehensive overview in this field is given in the article and basic principles are discussed.

GRAPHICAL ABSTRACT      

Comparative Study of Antimicrobial Activity of Silver,Gold, and Silver/Gold Bimetallic Nanoparticles Synthesized by Green Approach

Nanotechnology is one of the most recent technologies. It is uncertain whether the production of small-size nanoparticles (NPs) can be achieved through a simple, straightforward, and medicinally active phytochemical route. The present study aimed to develop an easy and justifiable method for the synthesis of Ag, Au, and their Ag/Au bimetallic NPs (BNPs) by using Hippeastrum hybridum (HH) extract, and then to investigate the effects of Ag, Au, and their Ag/Au BNPs as antimicrobial and phytotoxic agents. Ag, Au, and their Ag/Au BNPs were characterized by UV-visible spectroscopy, FT-IR spectroscopy, XRD, EDX, and SEM analysis. XRD analysis conferring to the face of face-centered cubic crystal structure with an average size of 13.3, 10.72, and 8.34 nm of Ag, Au, and Ag/Au BNPs, respectively. SEM showed that Ag, Au, and Ag/Au BNPs had spherical morphologies, with calculated nano measurements of 40, 30, and 20 nm, respectively. The EDX analysis confirmed the composition of elemental Ag signal of the HH-AgNPs with 22.75%, Au signal of the HH-AuNPs with 48.08%, Ag signal with 12%, and Au signal with 38.26% of the Ag/Au BNPs. The Ag/Au BNPs showed an excellent antimicrobial efficacy against Gram-positive Staphylococcus aureus, Actinomycetes meriye, Bacillus cereus, Streptococcus pyogenes, Methicillin-resistant Staphylococcus aureus, Micrococcus luteus, Streptococcus pneumonia, and Gram-negative Klebsiella pneumonia, Escherichia coli, and Serratia marcescens bacterial strains, as well as against three fungal strains (Aspergillus niger, Aspergillus fumigatus, and Aspergillus flavus) compared to HH extract, HH-AgNPs, and HH-AuNPs. However, further investigations are recommended to be able to minimize potential risks of application.     

Aqueous Gold Overgrowth of Silver Nanoparticles: Merging the Plasmonic Properties of Silver with the Functionality of Gold

To date, it has not been possible to combine the high optical quality of silver particles with the good chemical stability and synthetic convenience in a fully aqueous system, while simultaneously allowing chemical surface functionalization. We present a synthetic pathway for future developments in information, energy and medical technology where strong optical/electronic properties are crucial. Therefore, the advantages inherent to gold are fused with the plasmonic properties of silver in a fully aqueous Au/Ag/Au core–shell shell system. These nanoparticles inherit low dispersity from their masked gold cores, yet simultaneously exhibit the strong plasmonic properties of silver. Protecting the silver surface with a thin gold layer enables oxidant stability and functionality without altering the Ag‐controlled optical properties. This combines both worlds—optical quality and chemical stability—and is not limited to a specific particle shape.     

二氧化硅胶体晶体组装形貌研究

用原子力显微镜表征了二氧化硅胶体晶体的组装,探讨了二氧化硅微球用自然沉降法、抽滤法、溶剂挥发法组装时的组装行为,同时讨论了不同颗粒表面电位、不同溶剂介质及不同温度对其组装结果的影响。结果表明,颗粒表面电位是影响二氧化硅胶体晶体有序组装的重要因素之一。文中总结了最优的介质组成和温度条件,指出溶剂挥发法是较优的二氧化硅胶体晶体组装方法,其方法操作简单、周期短、得到的胶态晶体质量高,能在较大面积内高度有序。     

五氯酚免疫层析检测试纸条的研究

利用胶体金免疫层析技术建立了一种快速检测五氯酚(PCP)残留的方法。采用柠檬酸三钠还原法制备大小一致、分布均匀、粒径为20 nm的胶体金颗粒,以此标记五氯酚抗体,制备金标抗体。将五氯酚包被抗原和羊抗鼠二抗分别结合于硝酸纤维膜上,依次将型号Millipore135硝酸纤维膜、型号VL78金标垫、型号SB06样品垫及吸水纸组装于PVC底板上,组装成胶体金免疫层析检测试纸条。通过试纸条上颜色的深浅,检测样品中PCP的残留量。试纸条检出限为10 ng/mL,检测时间为5 min。该方法检测所需试剂已预先包被在试纸条上,操作简单、重复性好、成本低廉,可用于五氯酚的现场快速检测。     

混砂焙烧-火试金法测定文丘里泥中金、银含量

建立了文丘里泥中金、银含量的测定方法。将所称试样置于已有10g的石英砂中,并混匀;在750℃的条件下焙烧90min除去硒后,将冷却至室温的试料搅散,加入试金熔剂,用火试金法连续测定金、银的量。测定文丘里泥中金、银的相对标准偏差分别小于1.5%、0.70%,加标回收率金为98.6%～103%;银为96.7%～98.2%。结果稳定、可靠,且同时测定金、银含量。     

Application of Colloidal Gold to Fluorophotometric Determination of Human IgG

A method for the determination of human immunoglobulin G(IgG) based on a colloidal gold label by fluorospectrophotometry was developed. The sandwich immunoreaction among goat-anti-human IgG, human IgG and goat-anti-human IgG labeled with colloidal gold nanoparticles was applied in this experiment. First, a sandwich immunocomplex was formed on the surface of 96 well clear polystyrene high bind stripwellTM microplate. After the formation of the sandwich immunocomplex, a solution was added to dissociate the immunocomplex at room temperature. Then the solution of each well was transferred into the corresponding test tube. Thirdly, the rhodamine B solution was injected into each test tube. The rhodamine B chloraurate was extracted into ether that was measured with a spectrofluorometer. The experimental results indicate that the fluorescence intensity increased with the increase of human IgG concentration. The fluorescence intensity of rhodamine B chloraurate at 570 nm was proportional to the logarithm of human IgG concentration in a range from 10 to 5×105 ng/mL. It was shown that the determination of human IgG was easily made with the proposed fluorospectrophotometry.