Gas-phase synthesis and reactivity of a gold carbene complex

Electrospray ionization tandem mass spectrometry of a phosphonium ylid complex of gold produces an ion whose mass and gas-phase chemical reactivity indicate that it is a gold benzylidene complex. The complex, with a supporting NHC ligand, corresponds to a type of reactive intermediates which have been presumed to act in gold-catalyzed cyclopropanation reactions, but which have not been observed to date in solution or gas-phase experiments. A threshold CID experiment also yields thermochemical information on the formation of the gold carbene from the ylid complex precursor.     

Halogenation of (phosphine chalcogenide)gold(I) halides; some unexpected products

The monoselenide of 1,8-bis(diphenylphosphino)naphthalene reacts with (tht)AuCl to give the gold(III) system [(dppnAuSe)(2)](2+) 2Cl(-) (1); bromination of the bromogold(I) complex of the 1,2-bis(diphenylphosphino)methane monosulfide ligand furnishes the tribromide salt (2a) of a gold(III) cation [LAuBr(2)](+); bromination of the bromogold(I) complex of the 1,2-bis(diphenylphosphino)benzene monosulfide ligand leads to a mixed bromide/tetrabromoaurate salt (3) of a heterocyclic dication involving a [-PPh(2)-S-PPh(2)-](2+) moiety; analogous reactions of triphenylphosphine sulfide and selenide complexes lead to tetrabromoaurate salts (4a and 4b) of the (bromochalcogeno)phosphonium cations Ph(3)PEBr(+).     

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.     

Chalcogenide centred gold complexes

Chalcogenide-centred gold complexes are an important class of compounds in which a central chalcogen is surrounded by several gold atoms or gold and other metals. They have special characteristics such as unusual geometries, electron deficiency and properties such as luminescence or non-linear optical properties. The best known species are the trinuclear [E(AuPR(3))(3)](+), 'oxonium' type species, that have high synthetic applicability, not only in other chalcogen-centred species, but in many other organometallic derivatives. The aurophilic interactions play an important role in the stability, preference for a particular geometry and luminescence properties in this type of derivatives (critical review, 117 references).     

The elusive structures of pentakis[(triphenylphosphine)gold]ammonium(2+) bi

[Pentakis[(triphenylphosphine)gold(I)]ammonium(2+)] bis[(tetrafluoroborate)(1-)] was prepared from [tetrakis[(triphenylphosphine)gold(I)]-ammonium(1+)] [tetrafluoroborate(1-)] and [(triphenylphosphine)gold(I)] tetrafluoroborate in hexamethyl phosphoric triamide and tetrahydrofuran at 20 degrees C in 53% yield and crystallized from dichloromethane as the new solvate [[(Ph3P)Au]5N]3 [BF4]6 [CH2Cl2]4. The crystal structure of this product has been determined by single-crystal X-ray methods [monoclinic, P2(1/n), a = 34.200(3), b = 15.285(1), c = 53.127(3) A, beta = 107.262(2) degrees, V = 26521(3) A3, Z = 12, at 153 K]. The lattice contains three independent trinuclear dications that have no crystallographically imposed symmetry and are mutually similar in their molecular structure. The geometry of the [Au5N] core with pentacoordinate nitrogen atoms is intermediate between trigonal-bipyramidal and square pyramidal with severe distortions to minimize the Au-Au distances along some of the edges of the polyhedra. The three structures are thus different from that found previously in the tetrahydrofuran solvate [[(Ph3P)-Au]5N](BF4)2(C4H8O)2, where the geometry of the same trinuclear dication is closer to the trigonal-bipyramidal reference model. The new results are discussed in the light of the structures of tetra(gold)ammonium cations in salts of the type [[(Ph3P)Au]4N]+X- and of related tetra-, penta-, and hexacoordinate poly(gold)phosphonium, -arsonium, -sulfonium, and -selenonium cations.     

Fabrication of nano-network gold films via anodization of gold electrode and their application in SERS

We report here a green and facile one-step method to fabricate nano-network gold films of low roughness via anodization of gold electrodes in an aqueous solution of l-ascorbic acid (AA) or hydroquinone (H₂Q) at the oxidation peak potential. The preparation involves the formation of thin gold oxide layer by anodization of gold and its simultaneous and/or subsequent reduction by AA or H₂Q. The as-fabricated nano-network gold films show very strong SERS activity in comparison with the substrates prepared by some other electrochemical roughening methods.     

Determination of gold in gold ores

The gold content of placer gold flakes and gold bearing ores has been determined by instrumental neutron activation analysis /INAA/ and radiochemical neutron activation analysis /RNAA/. It was discovered that significant errors result in the instrumental method for gold flakes as small as 10 mg due to sample self-absorption of neutrons during irradiation. Reliable results were obtained, for both ore samples and gold flakes, by dissolving the samples in aqua regia prior to irradiation.     

Preparation and optical properties of worm-like gold nanorods

A type of worm-like nanorods was successfully synthesized through conventional gold nanorods reacting with Na2S2O3 or Na2S. The generated worm-like gold nanorods comprise shrunk nanorod cores and enwrapped shells. Therefore, a gold-gold sulfide core-shell structure is formed in the process, distinguishing from their original counterparts. The formation of the gold chalcogenide layers was confirmed by transmission electron microscopy and X-ray photoelectron spectroscopy. Experimental results showed that the thickness of the gold chalcogenide layers is controllable. Since the increase of shell thickness and decrease of gold nanorod core take place simultaneously, it allows one to tune the plasmon resonance of nanorods. Proper adjustment of reaction time, temperature, additives and other experimental conditions will produce worm-like gold nanorods demonstrating desired longitudinal plasmon wavelength (LPW) with narrow size distributions, only limited by properties of starting original gold nanorods. The approach presented herein is capable of selectively changing LPW of the gold nanorods. Additionally, the formed worm-like nanorods possess higher sensitive property in localized surface plasmon resonance than the original nanorods. Their special properties were characterized by spectroscopic methods such as Vis-NIR, fluorescence and resonance light scattering. These features imply that the gold nanorods have potential applications in biomolecular recognition study and biosensor fabrications.     

Directly monitoring the growth of gold nanoparticle seeds into gold nanorods

This paper describes the use of atomic force microscopy to directly image surface-attached 3-5 nm diameter gold nanoparticle seeds before and after seed-mediated growth into gold nanorods (Au NRs) and other shapes (spheres, triangles, and hexagons). Results show that Au NRs form from seeds growing in either one or two directions. A direct correlation exists between seed diameter and NR diameter; small diameter seeds form small diameter NRs. However, correlation between seed diameter and nanostructure shape or NR length is less evident. We describe our results in terms of growth mechanisms proposed in the literature and discuss possible reasons for the large size dispersity observed for surface-grown Au NRs. A better understanding of Au NR and other metal and semiconductor one-dimensional (1D) growth processes is necessary to improve synthesis, tailor their properties, and utilize 1D nanostructures for useful technological applications.     

Exploring the Coordination Properties of Phosphonium-Functionalized N-Heterocyclic Carbenes Towards Gold

Gold(I) complexes with N-heterocyclic carbene ligands functionalized with a pendant phosphonium moiety were synthesized by simple procedures. In particular, the simple addition of LiBr salt in the reaction media allows the formation of the NHC gold(I) mononuclear complexes, whilst in the absence of excess bromide ions the deprotonation of the methylene group in alpha position to the phosphonium group occurs, allowing the isolation of the dinuclear complexes with two C,C-bridging NHC-phosphonium ylide ligands. The complexes were characterized in solution with NMR spectroscopy and ESI-MS spectrometry, as well as in the solid state by means of single crystal X-ray diffraction analysis. Mononuclear gold(III) species were also isolated by Br₂ oxidative addition to the mononuclear gold(I) species and fully characterized. Preliminary results of the biological effects on MCF7 cancer cells are also reported.     

Interactions of zeatin with gold ions and biomimetic formation of gold complexes and nanoparticles

We report here a simple one-pot synthesis for the preparation of gold nanoparticles biomimetically using zeatin nanostructures. Zeatin, a plant phytohormone was self-assembled into nanospheres. Those nanospheres transformed into nanoribbons over a period of time upon formation of zeatin–gold (III) complexes in the presence of hydrogen tetrachloroaurate. Further, upon heating, gold nanoparticles were formed due to mineralization in the presence of zeatin nanofibers. The effect of pH on the self-assembly of zeatin and the formation of gold nanoparticles, was investigated. We also compared the preparation of gold nanoparticles in the presence of zeatin nanoribbons, using a known reducing agent such as hydrazine, which resulted in loss of morphology control and alignment of the gold nanoparticles. Thus zeatin nanoribbons act as templates which allow for size as well as alignment control for the gold nanoparticles. The materials obtained were analyzed using FTIR, absorbance spectroscopy as well as by transmission electron microscopy, EDX, SEM and AFM. The method involved here is a mild, green-synthetic process, which could be used for facile preparation of morphology controlled gold nanoparticles and may open up new avenues for device fabrications for a wide range of applications, particularly in optoelectronics and sensors.     

One-step synthesis and characterization of dendrimer-protected gold nanoparticles

We proposed an economic, convenient, and mild synthesis of dendrimer-protected gold nanoparticles by exposing a third-generation poly(propyleneimine) dendrimer-HAuCl₄ aqueous solution to sunlight without the additional step of introducing other reducing agents and protective agents. Most importantly, it is found that the size of the gold nanoparticles thus formed can be controlled by the molar ratio of the dendrimer to gold. The text was submitted by the author in English.     

Nanocrystalline gold and gold palladium alloy catalysts for chemical synthesis

Catalysis by gold has become one of the most studied new topics in chemistry in recent years, and yet for many gold acting as a catalyst is, perhaps, a most unlikely possibility since bulk gold is a relatively non-reactive, immutable, ductile metal that is prized for its great beauty and value rather than for the depth of its chemistry. However, when prepared in nanocrystalline form, as a collection of a few hundreds of atoms, it displays remarkable activity as a heterogeneous catalyst for a broad range of redox reactions. Of particular note is the ability of gold, either alone or alloyed with palladium, to catalyse selective oxidation reactions, e.g. alkene epoxidation, alcohol oxidation, and the direct synthesis of hydrogen peroxide by the hydrogenation of molecular oxygen. In this article the recent advances in this exciting new field are explored.     

Mechanism of trivalent gold reduction and reactivity of transient divalent and monovalent gold ions studied by gamma and pulse radiolysis

The detailed kinetics of the multistep mechanism of the Au(III) ion reduction into gold clusters have been investigated by radiation chemistry methods in 2-propanol. In particular, a discussion on the steady state radiolysis dose-dependence of the yields concludes to a comproportionation reaction of nascent gold atoms Au(0) with excess Au(III) ions into Au(II) and Au(I). This reaction should be achieved through Au(III) consumption before the coalescence of atoms Au(0) into gold clusters may occur. Then gold clusters catalyze the reduction of Au(I) by 2-propanol. It was also found that a long-lived Au(II) dimer, (Au(II))(2), was transiently formed according to the quantitative analysis of time-resolved absorbance signals obtained by pulse radiolysis. Then the disproportionation of Au(II) is intramolecular in the dimer instead of intermolecular, as usually reported. The yields, reaction rate constants, time-resolved spectra, and molar extinction coefficients are reported for the successive one-electron reduction steps, involving especially the transient species, such as Au(II), (Au(II))(2), and Au(I). The processes are discussed in comparison with other solvents and other metal ions.     

Direct evidence of oxidized gold on supported gold catalysts

Supported gold catalysts have drawn worldwide interest due to the novel properties and potential applications in industries. However, the origin of the catalytic activity in gold nanoparticles is still not well understood. In this study, time-of-flight secondary ion mass spectroscopy (TOF-SIMS) has been applied to investigate the nature of gold in Au (1.3 wt %)/gamma-Al2O3 and Au (2.8 wt %)/TiO2 catalysts prepared by the deposition-precipitation method. The SIMS spectrum of the supported gold catalysts presented AuO-, AuO2-, and AuOH- ion clusters. These measurements show direct evidence for oxidized gold on supported gold catalysts and may be helpful to gaining better understanding of the origin of the catalytic activity.     

The reaction of gold and dithizone

On thermodynamic grounds gold(III) and gold(I) are likely to oxidize dithizone rather than to form complexes. Conditions are described to obtain all the spectra previously ascribed to “gold dithizonate” both in a single system and separately. Oxidation products are responsible for several of the peaks, and it is unlikely that any of the species obtained is a gold dithizonate except possibly that giving the transitory peak at 490 nm. Analytical processes based on the reaction of gold and dithizone should be recognised as involving oxidation and treated with extreme caution.     

Electrocrystallization of rhodium clusters on thiolate-covered polycrystalline gold

This study reports on the electrochemical deposition of rhodium metal clusters on a polycrystalline gold electrode, modified with a monolayer of dodecanethiol through self-assembly from solution. The deposition process was investigated using cyclic voltammetry, chronoamperometry, and electrochemical quartz crystal microbalance. It is shown that the presence of the thiol monolayer drastically alters the nucleation and growth mechanism compared with the mechanism on the bare gold electrode. The small uncovered gold domains, located at the imperfections in the thiolate monolayer which are induced by the gold nanoroughness, act as nucleation sites for small rhodium clusters. At longer times, these clusters can outgrow the organic monolayer. The resulting surface morphology was characterized by scanning electron microscopy. Rhodium electrocrystallization on the bare gold substrate resulted in an ensemble of a very large amount of very small clusters that are difficult to distinguish from the gold roughness. In contrast, in the presence of a self-assembled monolayer (SAM) of dodecanethiol covalently attached to the gold electrode, the resulting deposit consisted of an ensemble of hemispherical particles. The size distribution of the rhodium particles obtained by using double step chronoamperometry was compared to the ones obtained with cyclic voltammetry and "classical" chronoamperometry. It is shown by X-ray photoelectron spectroscopy that the SAM is still present after rhodium deposition on the thiolate-covered gold substrate. Because the rhodium clusters are directly attached to the gold substrate and can thus easily be electrified, the resulting interface could be used as a composite electrode consisting of a random array of gold supported rhodium nano/microparticles separated from each other by an organic phase. On the other hand, it is shown that the SAM is easily removed by electrochemical oxidation without dissolving the rhodium clusters and, thus, leaving a different array of rhodium clusters on the gold surface compared with the topography obtained in the absence of the SAM. From this point of view, substrate modification with such "removable" organic monolayers was found to be an interesting tool to tune the nano- or microtopography of electrochemically deposited rhodium.     

Hydrophilicity of metal surfaces: Silver,gold and copper electrodes

In view of the current controversies about the hydrophilic character of polycrystalline silver and gold, an attempt is made here to clarify the situation by testing physical and electrochemical data using different approaches to the concept of hydrophilicity. Analysis shows that polycrystalline silver, gold and copper are hydrophobic metals. However it is stressed that this conclusion for silver, gold and copper refers to heterogeneous crystalline surfaces, while for other sp metals the hydrophilicity refers to relatively homogeneous surfaces. Recommended values of the work function are proposed for single-crystal surfaces of silver and gold.The validity different correlations between the surface potential of water molecules at the interface and various parameters is discussed for sp metals.The metal hydrophilicity is shown to be independent of the work function value. Moreover, the work function is not simply related to the surface electronegativity.     

金纳米粒子的表面修饰及生物应用进展

近年来纳米材料被广泛应用于生物医学、航空航天和精细化工等领域。构成纳米材料的纳米粒子具有小尺寸效应、表面效应和宏观量子隧道效应等性质。其中金纳米粒子由于其独特的荧光特性、良好的生物相容性和表面等离子共振等性质,被广大科研人员进行深入研究。例如,在生物医学领域,科研人员构建了一系列新型的金纳米比色传感器、光学探针及各类载药体系等。然而,目前金纳米粒子仍存在水分散性差、肾清除效率低和量子发射产率低等问题,限制了其广泛应用。因此,研究人员对金纳米粒子表面进行多样化修饰,从而能有效克服上述缺点。本文就目前主流配体表面修饰金纳米粒子的研究进展进行了详细总结,着重介绍了功能化金纳米粒子在生物成像、生物检测、生物治疗三方面的应用,最后对金纳米粒子的临床治疗机制的探索以及商业化的应用进行了展望,希望能为相关领域的研究者们提供新思路。     

Superconductivity in copper, silver, and gold compounds

High-temperature superconductivity exists in layered, square-planar cuprates, but is almost absent in most other Cu(II) compounds and in most Ag(II) and Au(II) compounds. Valence state II is quite unusual in silver and gold and often disproportionates to valence states I and III ("negative-U compounds"). The two-electron difference in oxidation state is suggestive of electron pairing, a prerequisite for superconductivity. In the present paper the connection between disproportionation and geometrical structure on one hand and superconductivity on the other is discussed by using the accepted theory for mixed valence complexes. It is concluded that absence of superconductivity in gold and silver compounds can be connected to the instability of oxidation state II and the large difference in equilibrium geometry between oxidation states I and III.