Gold nanoparticle size controlled by polymeric Au(I) thiolate precursor size

We developed a method in preparing size-controllable gold nanoparticles (Au NPs, 2-6 nm) capped with glutathione by varying the pH (between 5.5 and 8.0) of the solution before reduction. This method is based on the formation of polymeric nanoparticle precursors, Au(I)-glutathione polymers, which change size and density depending on the pH. Dynamic light scattering, size exclusion chromatography, and UV-vis spectroscopy results suggest that lower pH values favor larger and denser polymeric precursors and higher pH values favor smaller and less dense precursors. Consequently, the larger precursors led to the formation of larger Au NPs, whereas smaller precursors led to the formation of smaller Au NPs. Using this strategy, Au NPs functionalized with nickel(II) nitriloacetate (Ni-NTA) group were prepared by a mixed-ligand approach. These Ni-NTA functionalized Au NPs exhibited specific binding to 6x-histidine-tagged Adenovirus serotype 12 knob proteins, demonstrating their utility in biomolecular labeling applications.     

Facile synthesis of gold nanoparticles with narrow size distribution by using AuCl or AuBr as the precursor

Gold(I) halides, including AuCl and AuBr, were employed for the first time as precursors in the synthesis of Au nanoparticles. The synthesis was accomplished by dissolving Au(I) halides in chloroform in the presence of alkylamines, followed by decomposition at 60 degrees C. The relative low stability of the Au(I) halides and there derivatives eliminated the need for a reducing agent, which is usually required for Au(III)-based precursors to generate Au nanoparticles. Controlled growth of Au nanoparticles with a narrow size distribution was achieved when AuCl and oleylamine were used for the synthesis. FTIR and mass spectra revealed that a complex, [AuCl(oleylamine)], was formed through coordination between oleylamine and AuCl. Thermolysis of the complex in chloroform led to the formation of dioleylamine and Au nanoparticles. When oleylamine was replaced with octadecylamine, much larger nanoparticles were obtained due to the lower stability of [AuCl(octadecylamine)] complex relative to [AuCl(oleylamine)]. Au nanoparticles can also be prepared from AuBr through thermolysis of the [AuBr(oleylamine)] complex. Due to the oxidative etching effect caused by Br(-), the nanoparticles obtained from AuBr exhibited an aspect ratio of 1.28, in contrast to 1.0 for the particles made from AuCl. Compared to the existing methods for preparing Au nanoparticles through the reduction of Au(III) compounds, this new approach based on Au(I) halides offers great flexibility in terms of size control.     

基于Fe3O4@SiO2/Ni-NTA磁性微球的His-tag融合蛋白纯化体系的建立

合成了表面共价结合Ni-氨基三乙酸(Ni-NTA)基团的Fe3O4@ SiO2微球,这种磁性微球可用于分离含有His-tag标签的融合蛋白.微球中心由尺寸约402 nm的Fe3O4微粒组成,赋予了微球极好的磁性分离和离心分离的特性.应用Fe3O4@ SiO2/Ni-NTA磁性微球对含有6×His-tag(6聚组氨酸)标签的蛋白进行了分离纯化,结果表明,10 mg Fe3O4@ SiO2/Ni-NTA微球能够从10mL重组蛋白裂解液中纯化出约1 mg带有6×His-tag标签的融合蛋白.微球的高效分离效果使其能够用于含量较低的带有6×His-tag标签蛋白的分离纯化.     

Enzyme-purification and catalytic transformations in a microstructured PASSflow reactor using a new tyrosine-based Ni-NTA linker system attached to a polyvinylpyrrolidinone-based matrix

The synthesis of a Ni-nitrilotriacetic acid (Ni-NTA) attached via a new tyrosine-based linker matrix on monolithic crosslinked poly(vinyl benzyl chloride)/poly(vinylpyrrolidinone) is described. This matrix is incorporated inside a microstructured PASSflow reactor which was used for automatic purification and immobilisation of His(6)-tagged proteins. These could be used as stable and highly active biocatalysts for the synthesis of (R)-benzoin (6), (R)-2-hydroxy-1-phenylpropan-1-one (7) and 6-O-acetyl-D-glucal (17) in a flow-through mode.     

Facile syntheses of monodisperse ultrasmall Au clusters

During our effort to synthesize the tetrahedral Au20 cluster, we found a facile synthetic route to prepare monodisperse suspensions of ultrasmall Au clusters AuN (N < 12) using diphosphine ligands. In our monophasic and single-pot synthesis, a Au precursor ClAu(I)PPh3 (Ph = phenyl) and a bidentate phosphine ligand P(Ph)2(CH2)(M)P(Ph)2 are dissolved in an organic solvent. Au(I) is reduced slowly by a borane-tert-butylamine complex to form Au clusters coordinated by the diphosphine ligand. The Au clusters are characterized by both high-resolution mass spectrometry and UV-vis absorption spectroscopy. We found that the mean cluster size obtained depends on the chain length M of the ligand. In particular, a single monodispersed Au11 cluster is obtained with the P(Ph)2(CH2)3P(Ph)2 ligand, whereas P(Ph)2(CH2)(M)P(Ph)2 ligands with M = 5 and 6 yield Au10 and Au8 clusters. The simplicity of our synthetic method makes it suitable for large-scale production of nearly monodisperse ultrasmall Au clusters. It is suggested that diphosphines provide a set of flexible ligands to allow size-controlled synthesis of Au nanoparticles.     

Effect of pH and generation of dendron on single‐step synthesis of gold nanoparticles using PEGylated polyamidoamine dendron in aqueous medium

Three types of PEGylated polyamidoamine (PAMAM) dendrons were synthesized through PEGylation of primary amines at the periphery of second, third, and fourth generation dendrons. Au(III) precursors and the synthesized PEGylated PAMAM dendrons were mixed at various pHs to evaluate the effect of pH on gold nanoparticle (Au NP) synthesis by monitoring the change in surface plasmon resonance. The Au NP synthesis reaction was controlled by pH through the balance between protonated and deprotonated tertiary amines and the reactivity of Au(III) precursors. By using PEGylated PAMAM dendrons with higher generation, the obtained Au NPs had narrow size distribution with small average size because of the limitation of intermolecular space among PEGylated PAMAM dendrons for the growth to Au NP. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1391–1398, 2010     

Acetate coverage effect on the reactivity of vinyl acetate synthesis on Pd/Au alloy surfaces

Vinyl acetate (VA) synthesis on Pd/Au(111) and Pd/Au(100) surfaces has been systematically investigated through first-principles density functional theory (DFT) calculations. The DFT results showed that for VA synthesis, the ‘Samanos’ reaction mechanism (i.e., direct coupling of coadsorbed ethylene and acetate species and subsequent β-hydride elimination to form VA) is more favorable than the ‘Moiseev’ mechanism (i.e., ethylene first dehydrogenates to form vinyl species which then couple with the coadsorbed acetate species to form VA). More importantly, it was found the surface coverage of acetate has a significant effect on the reactivity of VA synthesis, and the activation energy of the rate-controlling step on Pd/Au(100) surface is smaller than that on Pd/Au(111) surface (0.88 vs. 0.95 eV), indicating the former is more active than the latter.     

A facile method for gold decoration of Te@CdTe nanorods in aqueous solution

Colloidal synthesis of metal-semiconductor hybrid nanostructures is mainly achieved in organic solution. In some applications of hybrid nanoparticles relevant in aqueous media, phase transfer of hydrophobic metal-semiconductor hybrid nanostructures is essential. In this work, we present a simple method for direct synthesis of water-soluble gold (Au) decorated Te@CdTe hybrid nanorods (NRs) at room temperature by using aqueous Te@CdTe NRs as templates, which were preformed by using CdTe nanocrystals (NCs) as precursor in the presence of hydrazine hydrate (N(2)H(4)). Our results showed that NRs were decorated with Au islands both on tips and along the surface of the NRs. The size and density of Au islands can be controlled by varying the amount of Au precursor (mixture of HAuCl(4) and thioglycolic acid (TGA)) and TGA/HAuCl(4) ratio. A possible growth mechanism for the Au decoration of Te@CdTe NRs is concluded as three steps: (1) the formation of AuTe(1.7) via the substitution reaction of Cd(2+) by Au(3+), (2) adsorption of Au-TGA complex onto the preformed AuTe(1.7) anchors and following reduction by CdTe and N(2)H(4), leading to the formation of small Au NCs, (3) Au NCs grow to bigger ones, followed by reduction of more Au precursor by N(2)H(4).     

SEC Characterization of Au Nanoparticles Prepared through Seed-Assisted Synthesis

In this paper we report the use of size-exclusion chromatography (SEC) for rapid determination of the sizes and size distributions of Au nanoparticles (NPs) prepared by seed-assisted synthesis. Analytical separation of Au NPs was performed in a polymer-based column of pore size 400 nm. We characterized the sizes and size distributions of the Au NPs by using 10 mM sodium dodecyl sulfate (SDS) as mobile phase and obtained a linear relationship (R ² = 0.986) between retention time and size of Au NPs within the range 9.8–79.1 nm; the relative standard deviations of these retention times were less than 0.3%. These separation conditions were used to characterize the sizes and size distributions of Au NPs prepared by seed-assisted synthesis. In addition to observing the elution times of the Au NPs we also simultaneously characterized their size-dependent optical properties by spectral measurement of the eluting peaks by use of an on-line diode-array detector (DAD), i.e., monitoring of the stability of the Au NP products. By using this approach we found the presence of SDS was beneficial in stabilizing the synthesized Au NPs. We also found that the volume of Au metal ions used affected the sizes of the final products. SEC seems an efficient tool for characterizing the sizes of NPs fabricated by seed-assisted synthesis.     

Bioassisted synthesis of catalytic gold/silica nanotubes using layer-by-layer assembled polypeptide templates

We report the bioassisted synthesis of gold nanoparticle/silica (Au NP/silica) tubes using layer-by-layer (LBL) assembled poly(L-lysine)/poly(L-tyrosine) (PLL/PLT) multilayer films deposited on the polycarbonate (PC) membrane pores as both mediating agents and templates. The novelty of this approach is the in situ synthesis of Au NP/silica tubes using PLL/PLT multilayer films for sequential growth of Au NPs and silicas. The experimental data revealed that the buildup of the LBL multilayer films was mainly driven by the formation of hydrogen bond and the polypeptide macromolecular assemblies adopted mainly β-sheet conformation. The as-prepared Au NP/silica tubes possessed promising catalytic activity toward the reduction of p-nitrophenol. The synthesis conditions such as the concentration of gold precursor and polypeptide molecular weight were found to influence the gold weight ratio and particle size in the tubes and the catalytic properties of the Au NP/silica tubes. This approach provides a facile, robust, and green method to obtain nonaggregated metal nanoparticles immobilized in porous oxide network at ambient conditions. Using the synergy between biomimetic or bioassisted synthesis of nanostructured materials and LbL assembly technique, a variety of structures such as films, tubes, and capsules comprising of multiple compositions can be obtained.     

Controllable synthesis of gold nanoparticles with ultrasmall size and high monodispersity via continuous supplement of precursor

Synthesis of monodisperse small Au nanoparticles in a controllable manner is of great importance for fundamental science and technical applications. Here, we report a "precursor continuous-supply" strategy for controllable synthesis of 0.9-3.3 nm Au nanoparticles with a narrow size distribution of 0.1-0.2 nm, using a weak reductant to slow-down the reducing rate of AuClPPh(3) precursor in ethanol. Time-dependent X-ray absorption and UV-Vis absorption measurements revealed that owing to the joint use of AuClPPh(3) and ethanol, the remnant AuClPPh(3) was self-supplied and the precursor concentration was maintained at a level near to its equilibrium solubility (ca. 1.65 mmol L(-1)) in ethanol. Hence the nucleation duration was extended that focused the initial size distribution of the Au clusters. With reaction going on for 58 min, most of AuClPPh(3) with a nominal Au concentration of 17.86 mmol L(-1) was converted to ethanol-soluble Au clusters with a size of about 1.0 nm, resulting in a high-yield synthesis.     

Heteropolynuclear phosphide complexes: phosphorus as unique atom bridging coinage metal centres

In this paper we describe the synthesis and reactivity of the diphenylphosphine derivatives [Au(C6F5)(PPh2H)] and trans-[Au(C6F5)2(PPh2H)2]ClO4. Reactions of the latter or the neutral [Au(C6F5)3(PPh2H)] with the appropriate Group 11 metal reagents (M = Au, Ag, Cu) in the presence of acetylacetonate afford a series of novel Au(III)-M phosphido-bridged complexes, which have been scarcely represented to date. The crystal structure of the tetranuclear [(Au(C6F5)2(mu-PPh2)2Ag)2] and the dinuclear [Au(C6F5)3(mu-PPh2)M(PPh3)] (M = Au,Ag) complexes were established by X-ray diffraction methods. The synthesis and deprotonating activity of the anionic gold(III) complex PPN[Au(C6F5)3(acac)] (PNN = [N(PPh3)2]+) was studied.     

Synthesis of Uniform Gold Nanorods with Large Width to Realize Ultralow SERS Detection

In this work, we successfully demonstrate high-yield synthesis of high-quality gold nanorods (Au NRs) with width ranging from 6.5 nm to 175 nm by introducing heptanol molecules as secondary templating agents during cetyltrimethylammonium bromide-templated, seeded growth method. The results show that an appropriate concentration of heptanol molecules not only alter the micellization behavior of CTAB in water, but also help silver ions impact the symmetry-breaking efficiency of additional Au−NP seeds in addition to enhancing the utilization of gold precursors. Moreover, the generality and versatility of the present strategy for synthesis of Au NRs with flexible controlled dimensions are further demonstrated by successful synthesis of Au NRs with the assistance of other fatty alcohols with properly long alkyl chains. Furthermore, when arrays of vertically aligned Au NRs with large width (AVA−Au_120×90 NRs) are used as SERS substrates, they can achieve the ultralow limit of detection for crystal violet (10⁻¹⁶ M) with good reliability and reproducibility, and the rapid detection and identification of residual harmful substances.     

Monitoring the Synthesis of Au Nanoparticles Using SEC

In this paper, it is demonstrated that size-exclusion chromatography (SEC) with SDS (10 mM) as the mobile phase can be used to rapidly determine the sizes of Au nanoparticles (NPs). It was found that standard particles at sizes ranging from 12.1 to 79.1 nm eluted in a linear manner with respect to the elution time. The reproducibility of the separation over the entire range of the calibration curve was high; the relative standard deviations of the elution times were less than 0.3%. Next, the separation conditions to characterize the sizes of Au NPs prepared through seed-assisted synthesis were employed. Using this approach, it was found that the rate of addition of the reducing agent influenced the sizes of the final products; for example, rapid addition of the reducing agent resulted in polydisperse Au NP products. SEC analysis revealed that the presence of NaOH in the synthesis medium decreased the sizes of the Au NPs dramatically. When using SEC to analyze Au NPs produced through seed-assisted synthesis, a good correlation existed between the sizes obtained using SEC and those provided by transmission electron microscopy (TEM). Based on these findings, SEC appears to be an efficient and accurate tool for characterizing the sizes of NPs fabricated through seed-assisted synthesis.     

Synthesis and electrospray mass spectrometry determination of thiolate-protected Au55(SR)31 nanoclusters

Since the pioneering work of Schmid et al. on phosphine-capped Au(55) clusters, the search for thiolated Au(55) has long been of major interest. This work reports the synthesis and electrospray ionization mass spectrometry (ESI-MS) evidence of Au(55)(SCH(2)CH(2)Ph)(31) clusters.     

Rapidly Characterizing the Growth of Au Nanoparticles by CE

In this paper, we describe a capillary electrophoresis (CE)-based method for the rapid characterization of Au nanoparticles (NPs) prepared through seed-assisted synthesis. We effected the CE separation of these Au NPs using a mixed buffer of sodium dodecyl sulfate (SDS; 70 mM) and 3-(cyclohexylamino)-1-propanesulfonic acid (CAPS; 10 mM) at pH 10.0 under an applied potential of 20 kV. A linear relationship (R ² = 0.985) existed between the electrophoretic mobilities and the sizes of the Au NPs within a range of diameters from 5.3 to 59.9 nm; the relative standard deviations of these electrophoretic mobilities were below 0.9%. When using these conditions to analyze the products of seed-assisted syntheses, we found that the rate of addition of the reducing agent affected the size distribution of the NPs dramatically. CE analysis also revealed that the presence of NaOH in the synthesis medium minimized the sizes of the Au NPs. When using these conditions to analyze the Au NPs produced through seed-assisted synthesis, a good correlation existed between the sizes obtained using CE and transmission electron microscopy (TEM). Based on these findings, CE appears to be an efficient tool for characterizing the sizes of NPs fabricated through seed-assisted synthesis.     

The role of oxidative etching in the synthesis of ultrathin single-crystalline Au nanowires

The fabrication of ultrathin single-crystal Au nanowires with high aspect ratio and that are stable in air is challenging. Recently, a simple wet-chemical approach using oleylamine has been reported for the synthesis of Au nanowires with micrometer length and 2 nm in diameter. Despite efforts to understand the mechanism of the reaction, an ultimate question about the role of oxygen (O(2)) during the synthesis remained unclear. Here we report that the synthesis of ultrathin Au nanowires employing oleylamine is strongly affected by the amount of O(2) absorbed in the reaction solution. Saturating the solution with O(2) leads to both a high-yield production of nanowires and an increase in their length. Nanowires with diameters of about 2 nm and lengths of 8 μm, which corresponds to an aspect ratio of approximately 4000, were produced. The role of oxygen is attributed to the enhanced oxidation of twin defects on Au nanoparticles formed in the first stage of the reaction. Understanding the role of oxidative etching is crucial to significantly increasing the yield and the length of ultrathin Au nanowires.     

Continuous Flow Synthesis of [Au(NHC)(Aryl)] (NHC=N-Heterocyclic Carbene) Complexes

The use of weak and inexpensive bases has recently opened promising perspectives towards the simpler and more sustainable synthesis of Au(I)-aryl complexes with valuable applications in catalysis, medicinal chemistry, and materials science. In recent years, continuous manufacturing has shown to be a reliable partner in establishing sustainable and controlled process scalability. Herein, the first continuous flow synthesis of a range of Au(I)-aryl starting from widely available boronic acids and various [Au(NHC)Cl] (NHC=N-heterocyclic carbene) complexes in unprecedentedly short reaction times and high yields is reported. Successful synthesis of previously non- or poorly accessible complexes exposed fascinating reactivity patterns. Via a gram-scale synthesis, convenient process scalability of the developed protocol was showcased.     

Highly Efficient Dehydrogenative Coupling of Hydrosilanes with Amines or Amides Using Supported Gold Nanoparticles

Hydroxyapatite‐supported gold nanoparticles (Au/HAP) can act as a highly active and reusable catalyst for the coupling of hydrosilanes with amines under mild conditions. Various silylamines can be selectively obtained from diverse combinations of equimolar amounts of hydrosilanes with amines including less reactive bulky hydrosilanes. This study also highlights the applicability of Au/HAP to the selective synthesis of silylamides through the coupling of hydrosilanes with amides, demonstrating the first example of an efficient heterogeneous catalyst. Moreover, Au/HAP shows high reusability and applicability for gram‐scale synthesis.     

Phosphoramidite gold(I)-catalyzed diastereo- and enantioselective synthesis of 3,4-substituted pyrrolidines

In this article the utility of phosphoramidite ligands in enantioselective Au(I) catalysis was explored in the development of highly diastereo- and enantioselective Au(I)-catalyzed cycloadditions of allenenes. A Au(I)-catalyzed synthesis of 3,4-disubstituted pyrrolidines and γ-lactams is described. This reaction proceeds through the enantioselective Au(I)-catalyzed cyclization of allenenes to form a carbocationic intermediate that is trapped by an exogenous nucleophile, resulting in the highly diastereoselective construction of three contiguous stereogenic centers. A computational study (DFT) was also performed to gain some insight into the underlying mechanisms of these cycloadditions. The utility of this new methodology was demonstrated through the formal synthesis of (-)-isocynometrine.