Effect of Latent Heat in Boiling Water on the Synthesis of Gold Nanoparticles of Different Sizes by using the Turkevich Method

The Turkevich method, involving the reduction of HAuCl₄ with citrate in boiling water, allows the facile production of monodisperse, quasispherical gold nanoparticles (AuNPs). Although, it is well‐known that the size of the AuNPs obtained with the same recipe vary slightly (as little as approximately 4 nm), but noticeably, from one report to another, it has rarely been studied. The present work demonstrates that this size variation can be reconciled by the small, but noticeable, effect that the latent heat in boiling water has on the size of the AuNPs obtained by using the Turkevich method. The increase in latent heat during water boiling caused an approximately 3 nm reduction in the size of the as‐prepared AuNPs; this reduction in size is mainly a result of accelerated nucleation driven by the extra heat. It was further demonstrated that, the heating temperature can be utilized as an additional measure to adjust the growth rate of AuNPs during the reduction of HAuCl₄ with citrate in boiling water. Therefore, the latent heat of boiling solvents may provide one way to control nucleation and growth in the synthesis of monodisperse nanoparticles.     

双子表面活性剂修饰金纳米流体的制备及稳定性

以双子表面活性剂丁烷-1,4(N-十四烷基-N,N-二甲基)溴化铵为表面修饰剂,石油醚/正丁醇为溶剂,抗坏血酸为还原剂,在不同温度条件下一步法分别得到油基-金纳米流体和水基-金纳米流体.对纳米流体中悬浮纳米金属颗粒的形貌、粒径、光谱性质等进行了表征.结果表明,p H=7~8的冰水浴条件下制得的纳米金颗粒具有亲油性,粒径均一且分散稳定性较好.采用紫外光谱法分别考察了极性有机溶剂和热作用对油基-金纳米流体稳定性的影响.结果表明,极性有机溶剂添加量超过30%(体积分数)时,对纳米流体稳定性的影响显著;随着热处理温度的升高,纳米流体中分散的纳米金颗粒的稳定时间逐渐缩短.     

Stability and Morphology of Gold Nanoisland Arrays Generated from Layer-by-Layer Assembled Nanoparticle Multilayer Films: Effects of Heating Temperature and Particle Size

This article reports the effects of heating temperature and composition of nanoparticle multilayer films on the morphology, stability, and optical property of gold nanoisland films prepared by nanoparticle self-assembly/heating method. First, nanoparticle-polymer multilayer films are prepared by the layer-by-layer assembly. Nanoparticle multilayer films are then heated at temperature ranging from 500 °C to 625 °C in air to induce an evaporation of organic matters from the films. During the heating process, the nanoparticles on the solid surface undergo coalescence, resulting in the formation of nanostructured gold island arrays. Characterization of nanoisland films using atomic force microscopy and UV-vis spectroscopy suggests that the morphology and stability of gold island films change when different heating temperatures are applied. Stable gold nanoisland thin film arrays can only be obtained after heat treatments at or above 575 °C. In addition, the results show that the use of nanoparticles with different sizes produces nanoisland films with different morphologies. Multilayer films containing smaller gold nanoparticles tend to produce more monodisperse and smaller island nanostructures. Other variables such as capping ligands around nanoparticles and molecular weight of polymer linkers are found to have only minimal effects on the structure of island films. The adsorption of streptavidin on the biotin-functionalized nanoisland films is studied for examining the biosensing capability of nanoisland arrays.     

Morphologies and surface plasmon resonance properties of monodisperse bumpy gold nanoparticles

The influence of the morphology of gold nanoparticles on the surface plasmon resonance was investigated experimentally and theoretically. Highly monodisperse bumpy gold nanoparticles of increasing size were synthesized, and the surface plasmon resonance wavelength shifted to longer wavelengths more rapidly with increasing particle size for bumpy particles than for spherical gold nanoparticles. The detailed surface morphology of bumpy gold nanoparticles was characterized by AFM, TEM, and SEM, and the optical properties were investigated on a single particle level. The comparison of the plasmon resonant properties between bumpy and spherical gold nanoparticles was also examined with a theoretical model.     

Simple reductant concentration-dependent shape control of polyhedral gold nanoparticles and their plasmonic properties

We report a facile seed-mediated method for the synthesis of monodisperse polyhedral gold nanoparticles, with systematic shape evolution from octahedral to trisoctahedral structures. The control over the particle growth process was achieved simply by changing the concentration of the reductant in the growth solution, in the presence of small spherical seed nanoparticles. By progressively increasing the concentration of the reductant used in the growth solution (ascorbic acid), while keeping the amount and type of added surfactant constant, the morphology of the gold nanoparticles was varied from octahedral to truncated octahedral, cuboctahedral, truncated cubic, cubic, and finally trisoctahedral structures. These nanoparticles were monodisperse in size, possessed similar volumes, and were naturally oriented so that their larger crystal planes were face down on quartz substrates when deposited from the solution. By adjusting the volume of gold seed nanoparticle solution added to a growth solution, the size of the simplest gold nanoparticles (with a highly symmetric cubic morphology) could be tuned from 50 ± 2.1 to 112 ± 11 nm. When other seed nanoparticles were used, the size of the cubic Au nanoparticles reached 169 ± 7.0 nm. The nanoparticle growth mechanism and the plasmonic properties of the resulting polyhedral nanoparticles are discussed in this paper.     

Bio‐interfaces—Interaction of PLL/HA Thick Films with Nanoparticles and Microcapsules

The interaction of biocompatible, exponentially grown films composed of poly‐L ‐lysine (PLL) and hyaluronic acid (HA) polymers with gold nanoparticles and microcapsules is studied. Both aggregated and non‐aggregated nanoparticle states are achieved; desorption of PLL accounts for aggregation of nanoparticles. The presence of aggregates of gold nanoparticles on films enables remote activation by near‐infrared irradiation due to local, nanometer confined heating. Thermally shrunk microcapsules, which are remarkably monodisperse upon preparation but gain polydispersity after months of storage, are also adsorbed onto films. PLL polymers desorbed from films interact with microcapsules introducing a charge imbalance which leads to an increase of the microcapsule size, thus films amplify this effect. Multifunctional, biocompatible, thick gel films with remote activation and release capabilities are targeted for cell cultures in biology and tissue engineering in medicine.     

Monodisperse sub-10 nm gold nanoparticles by reversing the order of addition in Turkevich method--the role of chloroauric acid

The Turkevich method for synthesizing gold nanoparticles, using sodium citrate as the reducing agent, is renowned for its ability to produce biocompatible colloids with mean size >10 nm. Here we show that monodisperse gold nanoparticles in the 5-10 nm size range can be synthesized by simply reversing the order of addition of reactants, i.e. adding chloroauric acid to citrate solution. Kinetic studies and electron microscopic characterization revealed that the reactivity of chloroauric acid, initial molar ratio of citrate to chloroauric acid (MR), and reaction mixture pH play an important role in producing monodisperse gold nanoparticles. Reversing the order of addition also enhanced the stabilization of nanoparticles at high MR values. Remarkably, the system exhibits a 'memory' of the order of addition, even when the timescale of mixing is much shorter than the timescale of synthesis.     

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.     

单分散球状纳米金颗粒的合成*

综述了近年来单分散球状金纳米颗粒的合成研究进展。分析了球状单分散金纳米颗粒的应用前景,介绍了单分散球状金纳米颗粒的主要合成方法如种子生长、回流熟化、尺寸选择沉淀分级以及电泳法等,评述了各种方法的优缺点。最后提出了单分散球状金纳米颗粒合成的一些问题,并展望了单分散球状金纳米颗粒的研究和发展方向。     

Flow-focused synthesis of monodisperse gold nanoparticles using ionic liquids on a microfluidic platform

A microfluidic device was used in tandem with an imidazolium-based ionic liquid to fabricate monodisperse gold nanoparticles (4.38 ± 0.53 nm) with excellent control over size and morphology.     

纳米金兔抗猪IgG化学发光探针的制备及表征

采用还原法制备了尺寸大小分别为4、14、30、41 nm的纳米金,优化了不同尺寸的纳米金兔抗猪IgG化学发光探针的制备条件。采用紫外-可见吸收光谱、透射电子显微镜和化学发光的方法对该探针进行了表征。结果表明纳米金兔抗猪IgG化学发光探针具有很好的单分散性和稳定性。本研究为纳米金兔抗猪IgG化学发光探针的应用奠定了基础。     

Size control in the synthesis of 1-6 nm gold nanoparticles via solvent-controlled nucleation

We report a facile synthetic route for size-controlled preparation of gold nanoparticles. Nearly monodisperse gold nanoparticles with core diameters of 1-6 nm were obtained by reducing AuP(Phenyl)(3)Cl with tert-butylamine borane in the presence of dodecanethiol in the solvent mixture of benzene and CHCl(3). Mechanism studies have shown that the size control is achieved by the solvent-controlled nucleation in which the nuclei concentration increases with increasing the fraction of CHCl(3), leading to smaller particles. It was also found that, following the solvent-controlled nucleation, particle growth occurs via ligand replacement of PPh(3) on the nuclei by Au(I)thiolate generated by the digestive etching of small particles. This synthetic strategy was successfully demonstrated with other alkanethiols of different chain length with which size-controlled, monodisperse gold nanoparticles were prepared in remarkable yield without requiring any postsynthesis treatments.     

Phase transfer of large gold nanoparticles to organic solvents with increased stability

In this paper, we describe a new procedure to phase transfer large gold nanoparticles (diameters > 45 nm) from aqueous solution to organic solvents. This is accomplished using a covalent amide coupling reaction that incorporates dicyclohexylamine (DCHA) headgroups on the surface of mercaptoacetic acid (MAA) functionalized gold nanoparticles. Gold nanoparticles are first synthesized in aqueous solution by the citrate-reduction method, and nanoparticle size is controlled by the molar ratio of the reducing agent (sodium citrate) and the gold precursor (KAuCl4). MAA is then adsorbed to the surface of the gold nanoparticles followed by an amide-coupling reaction to covalently attach DCHA to the surface-immobilized MAA. The bulky dicyclohexyl groups entropically stabilize gold nanoparticles in organic solvents. This procedure was used to reliably transfer gold nanoparticles with diameters between 45 and 100 nm from aqueous solution to organic solvents such as dimethyl sulfoxide and chloroform.     

Facile synthesis of gold nanoparticles capped with an ammonium-based chiral ionic liquid crystal

Herein, we describe a facile synthesis of stable chiral ionic liquid crystal (ILC)-capped gold nanoparticles. A new ILC containing a chiral cholesterol moiety having a terminal triethylammonium group was synthesised which exhibited an enantiotropic lamellar mesophase. Stable, monodisperse citrate-stabilised gold nanoparticles having a size of ~60 nm were prepared and the citrate ligands on the gold nanoparticles were replaced with chiral ILC through a two-phase ligand exchange process. The resulting chiral ILC-stabilised particles were characterised using UV–visible (UV–Vis) and transmission electron microscopy (TEM) studies. Different from the citrate-stabilised nanoparticles, the ligand exchanged gold nanoparticles were dispersible in organic solvent and resulting dispersion was stable for more than observed period of 3 months. Furthermore, the chiral ILC-decorated gold nanoparticles were found to be well dispersible in a nematic host without any aggregation and induced a vertical alignment of the nematic director.     

Microwave synthesis of polymer-embedded Pt-Ru catalyst for direct methanol fuel cell

Platinum-ruthenium nanoparticles stabilized within a conductive polymer matrix are prepared using microwave heating. Polypyrrole di(2-ethylhexyl) sulfosuccinate, or PPyDEHS, has been chosen for its known electrical conductivity, thermal stability, and solubility in polar organic solvents. A scalable and quick two-step process is proposed to fabricate alloyed nanoparticles dispersed in PPyDEHS. First a mixture of PPyDEHS and metallic precursors is heated in a microwave under reflux conditions. Then the nanoparticles are extracted by centrifugation. Physical characterization by TEM shows that crystalline and monodisperse alloyed nanoparticles with an average size of 2.8 nm are obtained. Diffraction data show that crystallite size is around 2.0 nm. Methanol electro-oxidation data allow us to propose these novel materials as potential candidates for direct methanol fuel cells (DMFC) application. The observed decrease in sulfur content in the polymer upon incorporation of PtRu nanoparticles may have adversely affected the measured catalytic activity by decreasing the conductivity of PPyDEHS. Higher concentration of polymer leads to lower catalyst activity. Design and synthesis of novel conductive polymers is needed at this point to enhance the catalytic properties of these hybrid materials.     

Polymer Cages as Universal Tools for the Precise Bottom‐Up Synthesis of Metal Nanoparticles

A template synthesis allows the preparation of monodisperse nanoparticles with high reproducibility and independent from self‐assembly requirements. Tailor‐made polymer cages were used for the preparation of nanoparticles, which were made of cross‐linked macromolecules with pendant thiol groups. Gold nanoparticles (AuNPs) were prepared in the polymer cages in situ, by using different amounts of cages versus gold. The polymer cages exhibited a certain capacity, below which the AuNPs could be grown with excellent control over the size and shape. Control experiments with a linear diblock copolymer showed a continuous increase in the AuNP size as the gold feed increased. This completely different behavior regarding the AuNP size evolution was attributed to the flexibility of the polymer chain depending on cross‐linking. Moreover, the polymer cages were suitable for the encapsulation of AgNPs, PdNPs, and PtNPs by the in situ method.     

Extinction coefficient of gold nanoparticles with different sizes and different capping ligands

Extinction coefficients of gold nanoparticles with core size ranging from approximately 4 to 40 nm were determined by high resolution transmission electron microscopy analysis and UV-vis absorption spectroscopic measurement. Three different types of gold nanoparticles were prepared and studied: citrate-stabilized nanoparticles in five different sizes; oleylamide-protected gold nanoparticles with a core diameter of 8 nm, and a decanethiol-protected nanoparticle with a diameter of around 4 nm. A linear relationship between the logarithms of extinction coefficients and core diameters of gold particles was found independent of the capping ligands on the particle surface and the solvents used to dissolve the nanoparticles. This linear relation may be used as a calibration curve to determine the concentration or average size of an unknown nanoparticle or nanoparticle-biomolecule conjugate sample.     

金纳米粒子的微波法合成及在蛋白质检测中的应用

通过对微波反应器中氯金酸和柠檬酸钠混合物进行直接加热,快速、一步合成了金纳米粒子.通过调节反应初始混合物中氯金酸与柠檬酸钠的比例,可获得不同粒径窄分散的金纳米粒子.进一步将所合成的金纳米粒子功能化,考察了其在蛋白质检测中的应用.     

An investigation of the thermal decomposition of gold acetate

The thermal decomposition characteristics of gold acetate to produce gold nanoparticles were investigated. A rapid and violent fragmentation of the gold acetate particles was observed at approximately 103±20°C when a rapid heating rate of 25°C min⁻¹ was used, leading to formation of nanosized spherical and partially coalesced gold particles. Particle size analysis was used to investigate possible relationships between the gold acetate crystallite size and the gold nanoparticles produced by thermal decomposition. The results indicate rapid (<0.14 ms) coalescence of the gold particles occurs for fragments in close proximity.     

Size‐Controlled Synthesis of Highly Monodisperse Gold Nanoparticles without a Size‐Selection and Long Range Ordered 2‐D Arrangement

A simple method is used to control the size of cetyltrimethylammoniumbromide‐protected Au nanoparticles by a reversal micelle in safe organic solvent. These Au nanoparticles can be evolved to highly monodisperse Au nanoparticles capped 1‐dodecanthiol in the 2, 3, and 5 nm diameter by refluxing at～160°C for 7 hours. Their ultraviolet visible spectroscopy (UV‐vis), x‐ray diffraction (XRD, transmission electron microscopy (TEM) showed that all the three different size gold nanoparticles(NPs) displayed high size homogenous properties and easy formed large areas of long ordered two‐dimensional arrangement at the air/solid interface.