Conductive properties of foam and cluster structures created from hexanthiol-passivated gold nanoparticles

The study of hexanethiol-passivated gold nanoparticles is reported. Depending on the age of the solution two kind of structures are obtained, “foam-like” in fresh solution and “cluster-like” few weeks after the solution preparation. Both kind of structures have been studied regarding to their structural and electrical properties. The cluster-like structures have shown lower electrical resistivity compared to foam-like ones. Some other factors like sonication, have shown to have no effect on the formation of one or another kind of structure.     

Optical and optoacoustic measurements of the absorption properties of spherical gold nanoparticles within a highly scattering medium

In the present paper the requirements for optical parameter characterization of absorbing materials located within a highly scattering medium has been addressed. The measurement scheme incorporates the optoacoustic technique where a single acoustic transducer is used to detect ultrasonic transients generated from laser irradiation. The absorbing medium is based on different concentrations of spherical gold nanoparticles (SGNP’s), these are currently being considered as non-toxic targeted optical contrast agents for both medical imaging and cancer therapeutics. In this paper we present results which demonstrate the two main advantages the optoacoustic technique has over other measurement schemes. These are the possibility to obtain information on the position and dimensions of absorbing bodies using a time of flight analysis (TOF) and secondly, the higher sensitivity of the optoacoustics compared to optical transmission techniques. The former advantage is of particular interest for imaging applications and the latter for detection and characterization of absorbing materials surrounded by high levels of high scattering mediums. We present for the first time the characterization of SGNP within a highly scattering medium. To further demonstrate the feasibility of the optoacoustic technique, the scattering coefficient of the surrounding medium has also been characterized.     

Hydrogen-assisted fabrication of spherical gold nanoparticles through sonochemical reduction of tetrachloride gold(III) ions in water

Spherical gold nanoparticles (AuNPs) were selectively synthesized through sonochemical reduction of tetrachloride gold(III) ions ([AuCl₄]⁻) in an aqueous solution of hydrogen tetrachloroaurate(III) tetrahydrate (HAuCl₄·4H₂O) with the aid of hydrogen (H₂) gas in the absence of any additional capping agents. On the other hand, various shaped-AuNPs such as spherical nanoparticles, triangular and hexagonal plates were formed from sonochemical reduction of [AuCl₄]⁻ in argon (Ar)-, nitrogen (N₂)- or oxygen (O₂)-purged aqueous [AuCl₄]⁻ solutions. The selective fabrication of spherical AuNPs assisted by H₂ gas is most likely attributed to the generation of hydrogen radicals (H) promoted by the reaction of H₂ introduced and hydrogen oxide radicals (OH) produced by sonolysis of water.     

Interaction of gold nanoparticles with nanosecond laser pulses: Nanoparticle heating

Theoretical and experimental results on the heating process of gold nanoparticles irradiated by nanosecond laser pulses are presented. The efficiency of particle heating is demonstrated by in-vitro photothermal therapy of human tumor cells. Gold nanoparticles with diameters of 40 and 100 nm are added as colloid in the cell culture and the samples are irradiated by nanosecond pulses at wavelength of 532 nm delivered by Nd:YAG laser system. The results indicate clear cytotoxic effect of application of nanoparticle as more efficient is the case of using particles with diameter of 100 nm. The theoretical analysis of the heating process of nanoparticle interacting with laser radiation is based on the Mie scattering theory, which is used for calculation of the particle absorption coefficient, and two-dimensional heat diffusion model, which describes the particle and the surrounding medium temperature evolution. Using this model the dependence of the achieved maximal temperature in the particles on the applied laser fluence and time evolution of the particle temperature is obtained.     

Sonosynthesis of gold nanoparticles from a geranium leaf extract

A rapid in situ biosynthesis of gold nanoparticles (AuNPs) is proposed in which a geranium (Pelargonium zonale) leaf extract was used as a non-toxic reducing and stabilizing agent in a sonocatalysis process based on high-power ultrasound. The synthesis process took only 3.5 min in aqueous solution under ambient conditions. The stability of the nanoparticles was studied by UV–Vis absorption spectroscopy with reference to the surface plasmon resonance (SPR) band. AuNPs have an average lifetime of about 8 weeks at 4 °C in the absence of light. The morphology and crystalline phase of the gold nanoparticles were characterized by transmission electron microscopy (TEM). The composition of the nanoparticles was evaluated by electron diffraction and X-ray energy dispersive spectroscopy (EDS). A total of 80% of the gold nanoparticles obtained in this way have a diameter in the range 8–20 nm, with an average size of 12 ± 3 nm. Fourier transform infrared spectroscopy (FTIR) indicated the presence of biomolecules that could be responsible for reducing and capping the biosynthesized gold nanoparticles. A hypothesis concerning the type of organic molecules involved in this process is also given. Experimental design linked to the simplex method was used to optimize the experimental conditions for this green synthesis route. To the best of our knowledge, this is the first time that a high-power ultrasound-based sonocatalytic process and experimental design coupled to a simplex optimization process has been used in the biosynthesis of AuNPs.     

Surface modification of gold nanoparticles and their monolayer behavior at the air/water interface

Gold nanoparticles were prepared by two different methods. The first method was chemically grafting the particles with different lengths of alkylthiol (C₆SH, C₁₂SH and C₁₈SH). For the second method, the Au particles were surface modified first by mercaptosuccinic acid (MSA) to render a surface with carboxylic acid groups which play a role to physically adsorb cationic surfactant in chloroform. This method was termed physical/chemical method. In the first method, the effects of alkyl chain length and dispersion solvent on the monolayer behavior of surface modified gold nanoparticles was evaluated. The gold nanoparticles prepared by 1-hexanthiol demonstrated the narrowest size distribution. Most of them showed narrower particle size distributions in chloroform than in hexane. For the physical/chemical method, the particles can spread more uniformly on the water surface which is attributed to the amphiphilic character of the particles at the air/water interface. However, the particles cannot pack closely due to the relatively weak particle-particle interaction. The effect of alkyl chain length was also assessed for the second method.     

Biosynthesis of gold nanoparticles using Capsicum annuum var. grossum pulp extract and its catalytic activity

Biological synthesis approach has been regarded as a green, eco-friendly and cost effective method for nanoparticles preparation without any toxic solvents and hazardous bi-products during the process. This present study reported a facile and rapid biosynthesis method for gold nanoparticles (GNPs) from Capsicum annuum var. grossum pulp extract in a single-pot process. The aqueous pulp extract was used as biotic reducing agent for gold nanoparticle growing. Various shapes (triangle, hexagonal, and quasi-spherical shapes) were observed within range of 6–37 nm. The UV–Vis spectra showed surface plasmon resonance (SPR) peak for the formed GNPs at 560 nm after 10 min incubation at room temperature. The possible influences of extract amount, gold ion concentration, incubation time, reaction temperature and solution pH were evaluated to obtain the optimized synthesis conditions. The effects of the experimental factors on NPs synthesis process were also discussed. The produced gold nanoparticles were characterized by transform electron microscopy (TEM), X-ray diffraction (XRD), energy dispersive X-ray (EDS) and Fourier Transform infrared spectroscopy (FTIR). The results demonstrated that the as-obtained GNPs were well dispersed and stable with good catalytic activity. Biomolecules in the aqueous extract were responsible for the capping and stabilization of GNPs.     

磁控溅射法制备金团簇纳米颗粒及性能表征

 采用磁控溅射法制备金团簇纳米颗粒,用透射电镜(TEM)、X射线衍射(XRD)、紫外可见光分光光度计(UV-Vis)和X射线光电子能谱(XPS)等分析手段对其表征,研究了金团簇纳米颗粒的形貌、颗粒度、结构、光吸收性质及物质成份。研究结果表明：制备的金团簇纳米颗粒呈球形,平均粒径在10 nm左右,粒径分布均匀,无团聚、氧化现象,颗粒的结构为面心立方。在519 nm处出现团簇颗粒的表面等离子共振吸收峰,测试得到Au(4f_7/2)和Au(4f_5/2)电子的结合能分别为83.3 eV和86.9 eV,并且没有出现金的氧化产物。     

Attachment of gold nanoparticles onto indium tin oxide surfaces controlled by adding citrate ions in a seed-mediated growth method

A simple approach to control the attachment of gold nanoparticles (AuNPs) onto the indium tin oxide (ITO) surfaces is reported. Adjusting the concentration of trisodium citrate in the Au colloid solution for the seeding process from 1 to 50 mM in the seed-mediated growth method, the dramatic changes in the SEM images and actual color were observed indicating the changes in nanostructures of AuNPs formed on the ITO surfaces. Whereas the attachment of smaller AuNPs with higher density were observed when 25 mM citrate ions were added in the seed solution, larger AuNPs were observed to attach at 50 mM. On the basis of this difference and the surface SEM images observed just after seeding, the roles of citrate ions were discussed. Consequently, it was inferred that the citrate ions affected the growth process as well as the seeding process. The repulsive power expected from the increased negative charges of citrate ions were not significant, but rather the dense attachment was promoted as the peculiar effect of citrate ions. Such control of the AuNPs attachment on ITO would be practically effective because the dense attachment can be performed by just changing the composition of the seed solution.     

Trapping and release of citrate-capped gold nanoparticles

An electrical method to trap and release charged gold nanoparticles onto and from the surface of gold electrodes modified by an alkanethiol self-assembled monolayer (SAM) is presented. To form electrodes coated with gold nanoparticles (GNPs), amine-terminated SAMs on gold electrodes were immersed in a solution of negatively charged citrate-capped GNPs. Accumulation of GNPs on the electrode surface was monitored by a decrease in the impedance of the SAM-modified electrode and by an increase in the electrochemical activity at the electrode as shown through cyclic voltammetry (CV). Electrostatic interactions between the GNPs and the amine-terminated SAM trap the GNPs on the electrode surface. Application of a subsequent negative bias to the electrode initiated a partial release of the GNPs from the electrode surface. Impedance spectroscopy, cyclic voltammetry, ultraviolet-visible (UV-Vis) spectroscopy and atomic force microscopy (AFM) were used to monitor and confirm the attraction of GNPs to and release from the aminealkanethiolated gold electrodes. This work describes a method of trapping and release for citrate-capped GNPs that could be used for on-demand nanoparticle delivery applications such as in assessing and modeling nanoparticle toxicology, as well as for monitoring the functionalization of gold nanoparticles.     

Spectroscopic characterization of core and shell regions in monolayer protected gold nanoparticles

We report studies on the structure of the metallic core and the alkyl cap layer in monolayer protected gold nanoparticles having sizes down to 1.6 nm. These particles are obtained by laser ablating gold targets in alkane-thiol solutions at different concentrations. The electronic structure of gold core and the vibrational properties of the capping hydrocarbon chains reveal effects connected with the nanosized nature of the particles.     

SERS intensity optimization by controlling the size and shape of faceted gold nanoparticles

In this work, we experimentally investigated the surface‐enhanced Raman spectroscopy (SERS) activity of faceted gold nanoparticles, which have been theoretically predicted to yield giant enhancements. Glycine was used to determine the SERS activity as a function of pH and ionic strength and to estimate the corresponding enhancement factor (EF). By optimizing the synthesis conditions of the flat prismatic nanoparticles, it was possible to control their size and shape. We demonstrate that the maximum SERS intensity increases with the edge length of the triangle, reaching a maximum EF of ∼10¹³ for 1.9 µm triangles (the largest tested). The corresponding glycine detection limit was as low as 10⁻¹² M , close to the single‐molecule threshold. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis and characterization of chemically anchored adenosine with PHEMA grafted gold nanoparticles

The synthesis of chemically anchored adenosine with biocompatible poly(2-hydroxylethyl methacrylate) grafted gold nanoparticles (Ado-i-PHEMA-g-AuNPs) was realized by employing a simple strategy. Disulfide-containing poly(2-hydroxylethyl methacrylate) (DT-PHEMA) was initially synthesized by atom transfer radical polymerization (ATRP). The formation of DT-PHEMA was confirmed by ¹H-NMR and FT-IR. The molecular weight and molecular weight distribution were found to be 9.6 kg/mol and 1.40 from GPC analysis. DT-PHEMA was subsequently used for the synthesis of PHEMA-g-AuNPs by a grafting to protocol. The grafting of DT-PHEMA on the surface of AuNPs was confirmed by FT-IR, TGA, XPS, and EDX analyses. The particle size of the PHEMA-g-AuNPs was found to be ca. 5.0 nm from HR-TEM analysis. Boronic acid was used for functionalization of PHEMA-g-AuNPs, which was then subjected for covalent immobilization with adenosine via strong interaction between free hydroxyl groups of adenosine and boronic acid. Characterization and properties of the Ado-i-PHEMA-g-AuNPs were investigated by taking advantage from FT-IR, XPS, EDX, and UV-visible spectroscopy. The Ado-i-PHEMA-g-AuNPs nanocomposite exhibits a surface plasmon resonance peak at 586 nm which is red shifted from AuNPs (521 nm), indicating significant changes of surface property upon PHEMA-adenosine immobilization onto the surface of AuNPs.     

Peristaltic blood flow with gold nanoparticles as a third grade nanofluid in catheter: Application of cancer therapy

Cancer is dangerous and deadly to most of its patients. Recent studies have shown that gold nanoparticles can cure and overcome it, because these particles have a high atomic number which produce the heat and leads to treatment of malignancy tumors. A motivation of this article is to study the effect of heat transfer with the blood flow (non-Newtonian model) containing gold nanoparticles in a gap between two coaxial tubes, the outer tube has a sinusoidal wave traveling down its wall and the inner tube is rigid. The governing equations of third-grade fluid along with total mass, thermal energy and nanoparticles are simplified by using the assumption of long wavelength. Exact solutions have been evaluated for temperature distribution and nanoparticles concentration, while approximate analytical solutions are found for the velocity distribution using the regular perturbation method with a small third grade parameter. Influence of the physical parameters such as third grade parameter, Brownian motion parameter and thermophoresis parameter on the velocity profile, temperature distribution and nanoparticles concentration are considered. The results pointed to that the gold nanoparticles are effective for drug carrying and drug delivery systems because they control the velocity through the Brownian motion parameter $N_b$ and thermophoresis parameter $N_t$. Gold nanoparticles also increases the temperature distribution, making it able to destroy cancer cells.     

Influence of Al-doped ZnO and Ga-doped ZnO substrates on third harmonic generation of gold nanoparticles

Principal role of substrate types on the nonlinear optical properties of Au NP was investigated. Third harmonic generation (THG) studies were carried out for Au NP deposited on the Al-doped ZnO (AuNP/AZO) and Ga-doped ZnO (AuNP/GZO) substrates at fundamental wavelength of 20 ns Er:glass laser (generating at 1540 nm wavelength) during photostimulation by the 532 nm 15 ns laser pulses. Sizes of Au NP were 5 nm, 10 nm, 20 nm, and 30 nm. The output signal was registered at 513 nm. The photoinduced power density was increased from 0 up to 800 MW/cm². So in our work we explore the role of the substrate on the optically stimulated non-linear optical properties during simultaneous photo stimulation near the inter-band transition. The results were studied depending on the type of substrate and the sizes of the deposited nanoparticles. The analysis was done within a framework of interaction between the photoinduced light and SPR wavelengths. Control of the photoinduced temperature was done.     

基于i-motifDNA构型变化和纳米金紫外-可见吸收光谱的pH测定研究

利用纳米金对DNA构型的区分效应设计了一种快速灵敏可视化的pH计。对i-motif DNA-纳米金体系的紫外可见吸收光谱变化进行了系统研究,考察了盐浓度、i-motif DNA浓度、四重体形成时间以及DNA序列对pH响应的影响。在既定条件下,纳米金的紫外-可见吸收光谱在pH 5.3～7.0范围内呈现规律性变化,在520nm处的吸光度逐渐增大,在700nm处的吸光度逐渐减小,纳米金的颜色逐渐由蓝紫色变化至红色。该pH计具有纳米金无需修饰、可视化、成本低、速度快等特点,有望用于某些pH值发生变化的生命过程的监测。     

Phyllanthin-assisted biosynthesis of silver and gold nanoparticles: a novel biological approach

Abstract  The anisotropic gold and spherical–quasi-spherical silver nanoparticles (NPs) were synthesized by reducing aqueous chloroauric acid (HAuCl₄) and silver nitrate (AgNO₃) solution with the extract of phyllanthin at room temperature. The rate of reduction of HAuCl₄ is greater than the AgNO₃ at constant amount of phyllanthin extract. The size and shape of the NPs can be controlled by varying the concentration of phyllanthin extract and thereby to tune their optical properties in the near-infrared region of the electromagnetic spectrum. The case of low concentration of extract with HAuCl₄ offers slow reduction rate along with the aid of electron-donating group containing extract leads to formation of hexagonal- or triangular-shaped gold NPs. Transmission electron microscopy (TEM) analysis revealed that the shape changes on the gold NPs from hexagonal to spherical particles with increasing initial concentration of phyllanthin extract. The Fourier transform infrared spectroscopy and thermogravimetric analyses reveal that the interaction between NPs and phyllanthin extract. The cyclic voltammograms of silver and gold NPs confirms the conversion of higher oxidation state to zero oxidation state. Graphical abstract  Anisotropic gold and silver nanoparticles were synthesized by a simple procedure using phyllanthin extract as reducing agent. The rate of bioreduction of AgNO₃ is lower than the HAuCl₄ at constant concentration of phyllanthin extract. The required size of the nanoparticles can be prepared by varying the concentration of phyllanthin with AgNO₃ and HAuCl₄.      

Evidences of the evolution from solid solution to surface segregation in Ni‐doped SnO2 nanoparticles using Raman spectroscopy

Ni‐doped SnO₂ nanoparticles, promising for gas‐sensing applications, have been synthesized by a polymer precursor method. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) data analyses indicate the exclusive formation of nanosized particles with rutile‐type phase (tetragonal SnO₂) for Ni contents below 10 mol%. The mean crystallite size shows a progressive reduction with the Ni content. Room‐temperature Raman spectra of Ni‐doped SnO₂ nanoparticles show the presence of Raman active modes and modes activated by size effects. From the evolution of the A_1g mode with the Ni content, a solubility limit at ∼2 mol% was estimated. Below that content, Raman results are consistent with the occurrence of solid solution (ss) and surface segregation (seg.) of Ni ions. Above ∼2 mol% Ni, the redshift of A_1g mode suggests that the surface segregation of Ni ions takes place. Disorder‐activated bands were determined and their integrated intensity evolution with the Ni content suggest that the solid‐solution regime favors the increase of disorder; meanwhile, that disorder becomes weaker as the Ni content is increased. Copyright © 2010 John Wiley & Sons, Ltd.     

The bonding geometry of alkylsilanes on gold: Relation to surface pattern development and STM image contrast

The adsorption of methylsilane (MeSiH₃) on Au(1 1 1) was investigated using density functional theory (DFT) within a generalized gradient approximation (GGA). Two preferred chemisorption sites are identified: the hollow site and an atop site with an ejected gold substrate atom. Both of these configurations result in a tetracoordinate Si with a distorted tetrahedral geometry. The energy of adsorption is calculated allowing an analysis of the preferred binding geometry as a function of coverage. The relation of the supermolecular length scale pattern that emerges from a spinodal decomposition of the two phases arising from the two binding geometries is discussed. The pattern observed in the STM images is shown to be consistent with the local density of states calculated for the two different binding geometries.     

Preparation of nano-gypsum from anhydrite nanoparticles: Strongly increased Vickers hardness and formation of calcium sulfate nano-needles

The preparation of calcium sulfate by flame synthesis resulted in the continuous production of anhydrite nanoparticles of 20–50 nm size. After compaction and hardening by the addition of water, the anhydrite nanoparticles reacted to nano-gypsum which was confirmed by X-ray diffraction, diffuse reflectance IR spectroscopy and thermal analysis. Mechanical properties were investigated in terms of Vickers hardness and revealed an up to three times higher hardness of nano-gypsum if compared to conventional micron-sized construction material. The improved mechanical properties of nano-gypsum could in part be due to the presence of calcium sulfate nano-needles in the nano-gypsum as showed by electron microscopy.