三苯基磷氯金的电化学合成

以高纯金为牺牲阳极,在三苯基磷与浓盐酸的乙腈溶液中,用电化学方法合成了三苯基磷氯金(Au(PPh3) Cl),并经适当的纯化处理获得了Au(PPh3) Cl白色针状晶体.元素分析、红外光谱和X射线衍射分析结果表明,所制备的产物为Au(PPh3) Cl纯相,同时还对Au(PPh3) Cl电化学合成机理及相关实验条件的影响进行了讨论.     

乙酰丙酮三苯基膦羰基铑（I）的合成与表征

乙酰丙酮三苯基膦羰基铑(I)广泛用做羰基合成醇化工过程的催化剂。作者以RhCl3·nH2O为原料通过2步合成了该化合物,总收率为91%。用元素分析、红外光谱及核磁共振氢谱对该化合物进行了分析和结构表征,结果与文献报道一致。本工艺操作简单,可大规模批量生产,产品已成功应用于国内某大型羰基合成醇装置。     

系列金(I)有机膦化合物的合成

以氯金(III)酸(HAuCl4)为起始原料,经过两步反应合成了3种有机膦氯化金化合物,产率均在95%以上。首先HAuCl4与二甲基硫醚(Me2S)反应,制备二甲基硫醚氯化金(I)中间体;然后与有机膦,包括三苯基磷(PPh3)、双(二苯基膦)二茂铁(dppf)、1,2-双(二苯基膦)乙烷(dppe)反应,合成了的三苯基膦氯化金(I)[AuCl(PPh3)]等有机膦氯化金,[AuCl(PPh3)]与三氟甲烷磺酸银(AgSO3CF3)反应,可进一步获得三氟甲烷磺酸三苯基膦金(I)[(CF3SO3)][Au(PPh3)]。     

Design of luminescent sulfur-containing polynuclear gold(I) complexes for advanced nanomaterials and chemosensors

A series of high-nuclearity gold(I) sulfido complexes with bridging diphosphine ligands have been synthesized and isolated, with the general formulae of [Au₁₀(μ-P^P)₄(μ₃-S)₄]X₂ and [Au₁₂(μ-P^P)₄(μ₃-S)₄]X₄ (P^P = diphosphine; X = PF₆ or ClO₄). Intense green and orange emissions were observed upon excitation at λ > 350 nm both in the solid state and in solutions. The green emission has been attributed to originate from excited states derived from the metal-perturbed intraligand (IL) transition while the orange emission arises from the ligand-to-metal-metal bond charge-transfer (LMMCT; S(Au...Au) states. The switching on and off of the LMMCT emission in a series of dinuclear gold(I) thiolate complexes with crown ether pendants induced by ion-binding has been demonstrated, and this provides a new strategy for the design of luminescence signalling and chemosensing devices in optoelectronics and sensor technology.     

Gold(I) and gold(III) complexes with anionic oxygen donor ligands: hydroxo, oxo and alkoxo complexes

The chemistry of gold(I) and gold(III) hydroxo, oxo and alkoxo complexes containing organic co-ligands is reviewed. Due to the high reactivity of the gold-oxygen bond most of these species can be employed as useful intermediates in many important processes. Alkoxides are by far the most numerous class among these species, and both gold(I) and gold(III) complexes are known with a variety of alkoxides. The recent discovery of the catalytic activity of some gold(I) and gold(III) fluoroalkoxides has enlivened the interest towards this class of compounds leading to new applications for previously known complexes, as is the case for a gold(III) siloxo complex which has found use as a precursor for CVD, as well as for the synthesis of new alkoxo derivatives. Another well represented and well known class of compounds are the gold(I) oxo complexes [O(AuPR₃)₃]⁺ which are the most effective aurating reagents. Gold(III) oxo complexes have been synthesized only recently and much of their chemistry is still largely to be explored. Preliminary studies suggest their potential in the transfer of oxygen atoms. Finally, some cationic gold(III) hydroxo complexes are found to display significant,and in some cases relevant, cytotoxic effects on cancer cell lines.     

Synthesis of non-spherical gold nanoparticles

Non-spherical gold nanoparticles such as rods (short, long) (1,2), wires, cubes (3), nanocages (4), (multi-)concentric shells (5), triangular prisms (6–7), as well as other more exotic structures such as hollow tubes, capsules (6), even branched nanocrystals (8–9) have garnered significant research attention in the past few years. They exhibit unique and fine-tuned properties which either strongly differ or are more pronounced from those of symmetric, spherical gold nanoparticles. Their unusual optical and electronic properties, improved mechanical properties and specific surface-enhanced spectroscopies make them ideal structures for emerging applications in photonics, electronics, optical sensing and imaging, biomedical labelling and sensing, catalysis and electronic devices among others (10,11,12,13,14,15,16,17,18). Furthermore, some of these anisotropic nanoparticles enable elucidation of the particle growth mechanism, which in turn makes it possible to predict and systematically manipulate the final nanocrystal morphology (8,19-20). Finally, these anisotropic gold nanomaterials provide templates for further generation of novel materials (21,22).     

Synthesis of oligo(para-phenylenevinylene) methyl thiols for self-assembled monolayers on gold surfaces

All-trans oligo(para-phenylenevinylene) (OPV) methyl thiols of a two-ring phenylene-vinylene dimer and a three-ring trimer have been synthesized to prepare self-assembled monolayers (SMS) onto an Au(1 1 1) surface. The molecular level morphologies of the monolayers prepared on Au surfaces were probed by scanning tunneling microscopy (STM) or atomic force microscopy (AFM). The soluble dimer formed a highly ordered structure lying down on the Au surfaces. The molecules of trimer stand slantwise on the Au surfaces, but the structure of monolayers is less ordered. Another longer OPV methyl thioacetate, a slightly soluble four-ring tetramer, has also been synthesized. Although it was difficult for aggregative molecules of the longer OPV to self-assemble on Au, we could successfully insert the tetramer into tetradecane-1-thiol monolayers on Au surfaces by an exchange reaction. The mixture monolayer showed that the isolated tetramer was adsorbed almost vertically on the Au surfaces.     

用CTAB/TBP体系从碱性氰化液中萃取低浓度Au(I)

以TBP为萃取剂, 用新型的柱状萃取装置对水相中加入与Au(I)等摩尔CTAB(十六烷基三甲基溴化铵)的低浓度氰化金溶液进行了萃取研究, 考察了水相中添加CTAB、有机相TBP的体积、盐析剂NaCl浓度等对TBP萃取Au(I) 性能的影响以及载金有机相中金的反萃取. 结果表明: 在水相中添加CTAB后, TBP对低浓度金的萃取性能大幅度提高; 50.L含金浓度约为10.mg/L的氰化金溶液经3级萃取试验后, 金的萃取率大于95%, 萃余相浓度小于0.5×10-6. 用硫氰化钾对含金浓度约为3.g/L的载金有机相进行了反萃取研究, 当KSCN浓度大于3.mol/L时, 对金的反萃率大于93%.     

用CTAB／TBP体系从碱性氰化液中萃取低浓度Au（Ⅰ）

以TBP为萃取剂, 用新型的柱状萃取装置对水相中加入与Au(I)等摩尔CTAB(十六烷基三甲基溴化铵)的低浓度氰化金溶液进行了萃取研究, 考察了水相中添加CTAB、有机相TBP的体积、盐析剂NaCl浓度等对TBP萃取Au(I) 性能的影响以及载金有机相中金的反萃取. 结果表明 在水相中添加CTAB后, TBP对低浓度金的萃取性能大幅度提高; 50.L含金浓度约为10.mg/L的氰化金溶液经3级萃取试验后, 金的萃取率大于95%, 萃余相浓度小于0.5×10-6. 用硫氰化钾对含金浓度约为3.g/L的载金有机相进行了反萃取研究, 当KSCN浓度大于3.mol/L时, 对金的反萃率大于93%.     

Synthesis,photophysical and electrophosphorescent properties of a novel fluorinated rhenium(I) complex

A novel fluorinated rhenium complex, i.e., Re-BFPP (BFPP, 2, 3-bis(4-fluorophenyl)pyrazino[2,3-f][1,10]phenanthroline) was designed, synthesized and characterized by ¹H NMR and mass spectroscopy. The light-emitting and electrochemical properties of this complex were studied. The organic light-emitting diodes (OLEDs) employing Re-BFPP as a dopant emitter with the structures of ITO/m-MTDATA (10 nm)/NPB (20 nm)/CBP: X wt.% Re-BFPP (30 nm)/Bphen (10 nm)/Alq₃ (30 nm)/LiF (1 nm)/Al (100 nm) were successfully fabricated and a broad electroluminescent peak at 553 nm was observed. The 10 wt.% Re-BFPP doped device exhibited the maximum luminance of 6342 cd/m² and a peak current efficiency of 17.9 cd/A, corresponding to the power efficiency of 8.1 lm/W.     

Effect of the crystal face orientation and alloying with gold on the properties of thin anodic films of Ag(I) oxide: I. Photocurrent

The anodic formation of nano-size anodic films of Ag(I) oxide on polycrystalline silver and Ag-Au alloys, as well as on low-index monocrystalline silver faces in 0.1 M KOH, is studied. Based on the data of photocurrent measurements, the n-kind of the oxide film conductivity is determined. Replacing the polycrystalline silver with monocrystals, as well as adding a small amount of gold atoms to its lattice (X _[Au] <= 4 at. %), results in substantial structure ordering of the oxide due to the decrease in the deviation from the stoichiometric composition. The structure-dependent parameters of Ag(I) oxide (the optical absorption coefficient α, the concentration of donor defects N _D, the width of the spatial charge region W, and the Debye screening length L _D) are determined by the silver crystal face orientation, the gold content, and the film formation potential. At E = 0.52 V, the series of changes in these characteristics correlate with the series of reticular density. An increase in E breaks the series and increases the deviation of the composition from the stoichiometric Ag₂O composition.     

A review on fulminating gold (Knallgold)

Expensive and explosive! The reaction of ammonia and gold(III) compounds leads to explosive products known as “fulminating gold”. Gold scientists should be aware of the potential hazards involved in the reaction of these starting materials. Herein, a historic and scientific review on this fascinating substance is presented. Fulminating gold has been known since medieval times, but cannot be fully characterized due to its polymeric and heterogeneous character. Magnetic measurements confirm previous EXAFS analyses that the gold atoms have a square planar coordination environment (AuN₄-moieties that are party connected and form a 3-dimensional network). The explosive properties and resulting safety instructions are discussed in detail as well.     

Kinetic peculiarities of anodic dissolution of copper and its gold alloys accompanied by the formation of insoluble Cu(I) products

The kinetics of anodic dissolution of Cu and Cu-Au alloys (0.1-30 at.% Au) in aqueous chloride-containing universal buffer mixture (pH 1.25-11.90) in the potential range of insoluble Cu(I) products formation has been examined using the technique of multicyclic voltammetry and chronoamperometry of stationary and rotating electrodes. After the formation of anodic film, mass transport controls the dissolution; the phase where the transport is localised depends on the nature of the film, pH of the solution and the alloy composition. The initial stage of CuCl formation on Cu and low-concentration Cu-Au alloys is controlled by 2D-nucleation.     

双(二甲氧基苯基膦)二氯化钯(Ⅱ)的合成及化学结构表征

以氯亚钯酸钠、双甲氧基苯基膦酸盐为起始原料,通过配位取代反应合成了大配体C-C偶联催化剂双(二甲氧基苯基磷)二氯化钯(Ⅱ)(Pd Cl2[P(OMe)2Ph]2)。优化的一步合成条件为:在氩气保护下,向双甲氧基苯基膦酸盐的四氢呋喃溶液中滴加0.5倍摩尔分数的氯亚钯酸钠水溶液,50℃反应得到配合物,产率为96.5%。采用核磁共振(1H NMR)及单晶X射线衍射(XRD)对产物化学结构进行测定和解析。1H NMR显示,2个苯环及4个甲氧基上的氢核信号的化学位移、峰面积与目标化合物对应一致;单晶XRD确定其晶体为单斜晶系空间群为C2/c,获得了相应的键长和键角参数。     

Phase studies on the quasi-binary thallium(I) selenide-thallium(I) telluride system

The phase diagram for the system Tl₂Te-Tl₂Se has been determined on the basis of the results of studies by means of common thermal analysis. The diagram has been compared with diagrams published earlier. Some regularities have been presented for the quasi-binary chalcogenide systems with common cation.     

Bioleaching of refractory gold ore （ Ⅲ ）——Fluid leaching Jinya refractory gold concentrate by Thiobacillus ferrooxidans

A novel fluidized-bed reactor was designed and installed for bloleaching in a semi-continuous way, by which a process for biuleaching-cyanidation of Jinya refractory gold arsenical concentrate was studied. The arsenic extraction rate reaches 82.5 % after 4-day batch biooxidation of the concentrate under the optimized condition of pH 2.0, ferric ion concentration 6.Sg/L and pulp concentration 10%. And leached rate of gold in the following cyanida.tion is over 90%. The parameters of three series fluidized-bed reactors exhibit stability during the semi-continuous bioleaching of the concentrate.Armmic in the concentrate can be got rid of 91% after 6-day leaching. Even after 4 days, 82% of arsenic extraction rate was still obtained. The recovery rates of gold are 92 % and 87.5 % respectively in cyaniding the above bioleached residues.The results will provide a base for further commercial production of gold development.     

Phase studies on the quasi-binary thallium(I) selenide-thallium(I) telluride system

The phase diagram for the system Tl₂Te-Tl₂Se has been determined on the basis of the results of studies by means of common thermal analysis. The diagram has been compared with diagrams published earlier. Some regularities have been presented for the quasi-binary chalcogenide systems with common cation.