Synthesis of Highly Substituted γ‐Butyrolactones by a Gold‐Catalyzed Cascade Reaction of Benzyl Esters

Easily accessible benzylic esters of 3‐butynoic acids in a gold‐catalyzed cyclization/rearrangement cascade reaction provided 3‐propargyl γ‐butyrolactones with the alkene and the carbonyl group not being conjugated. Crossover experiments showed that the formation of the new C?C bond is an intermolecular process. Initially propargylic–benzylic esters were used, but alkyl‐substituted benzylic esters worked equally well. In the case of the propargylic–benzylic products, a simple treatment of the products with aluminum oxide initiated a twofold tautomerization to the allenyl‐substituted γ‐butyrolactones with conjugation of the carbonyl group, the olefin, and the allene. The synthetic sequence can be conducted stepwise or as a one‐pot cascade reaction with similar yields. Even in the presence of the gold catalyst the new allene remains intact.     

Probing the Catalytic Activity of Reduced Graphene Oxide Decorated with Au Nanoparticles Triggered by Visible Light

Hybrid materials in which reduced graphene oxide (rGO) is decorated with Au nanoparticles (rGO–Au NPs) were obtained by the in situ reduction of GO and AuCl₄^?_(aq) by ascorbic acid. On laser excitation, rGO could be oxidized as a result of the surface plasmon resonance (SPR) excitation in the Au NPs, which generates activated O₂ through the transfer of SPR‐excited hot electrons to O₂ molecules adsorbed from air. The SPR‐mediated catalytic oxidation of p‐aminothiophenol (PATP) to p,p′‐dimercaptoazobenzene (DMAB) was then employed as a model reaction to probe the effect of rGO as a support for Au NPs on their SPR‐mediated catalytic activities. The increased conversion of PATP to DMAB relative to individual Au NPs indicated that charge‐transfer processes from rGO to Au took place and contributed to improved SPR‐mediated activity. Since the transfer of electrons from Au to adsorbed O₂ molecules is the crucial step for PATP oxidation, in addition to the SPR‐excited hot electrons of Au NPs, the transfer of electrons from rGO to Au contributed to increasing the electron density of Au above the Fermi level and thus the Au‐to‐O₂ charge‐transfer process.     

Determination of ultra-trace gold in natural water by graphite furnace atomic absorption spectrophotometry after in situ enrichment with thiol cotton fiber

A simple method of determining ultra-trace Au in natural water was presented by using graphite furnace atomic absorption spectrophotometry (GFAAS) after in situ enrichment with thiol cotton fiber (TCF). The sample solution was adjusted to pH 1.5-2.0 with HCl, then the water sample was passed through a column packed with 0.10-0.20 g TCF and the flow rate was controlled at 20-40 ml min⁻¹. The effects of interferences, such as complexing and oxidizing agents and other elements adsorbed on TCF were overcome by chemical treatments prior to the desorption of Au. The adsorbed Au was adsorbed with 2.0 ml hot acid, then it was extracted with 1.00 ml methyl isobutylketone (MIBK). For a 5 l water sample, the detection limit of Au is 0.02 ng l⁻¹. The relative standard deviation (R.S.D.) for the determination of 1.44 ng l⁻¹ Au was 9.4%.The method was applied to determine ultra-trace Au both in suspended phase and soluble phase in natural water, the concentrations of total Au in natural water samples range from 0.51 to 67.82 ng l⁻¹. The recovery of added 0.50-6.00 ng l⁻¹ Au was 80-95%. The method is useful in prospecting for Au deposits by means of hydrogeochemical methods. The enrichment is carried out in the field, and then the determination of Au is completed later in the laboratory.     

Bi12TiO20纳米粉体的制备及其光吸收特性研究

以钛酸四丁酯和硝酸铋为原料 ,利用化学溶液分解法制备了Bi12 TiO2 0 纳米多晶粉体 .采用XRD和TEM对其结构和形貌进行了表征 .结合热重 差热 (TG DTA)分析 ,探讨了Bi12 TiO2 0 晶相的形成机理 .通过UV Vis漫反射谱的测定 ,研究了Bi12 TiO2 0 纳米晶粉体的光吸收特性 .结果显示 ,从组成为化学计量比的前驱液中可以很容易制得纯Bi12 TiO2 0 纳米晶粉体 ,该Bi12 TiO2 0 纳米晶粉体呈现了在很宽的波长范围内 (5 6 0～ 385nm )对光的吸收的特性 .     

Friedel-Crafts alkylation of indoles with epoxides catalyzed by nanocrystalline titanium(IV) oxide

Friedel-Crafts alkylation of indoles with epoxides to afford 3-alkyl indole derivatives at room temperature with moderate to good yields and high regioselectivity using nanocrystalline titanium(IV) oxide catalyst is described.     

无催化纳米氧化锌的制备及其光学性质研究

本文采用无催化剂直接蒸发高纯Zn粉,在800℃氧气氛条件下,在Si(111)衬底上生长得到以四角状为主的纳米ZnO(T-ZnO)。T-ZnO纳米线每个角约互成110°,长度约为1.5μm,直径100nm左右;Raman分析表明E2(H)普遍存在于各形态的ZnO;光致发光光谱表明,T-ZnO纳米线的光致发光除了与材料性质有关,还与杂质缺陷有关,蓝绿光带是ZnO的缺陷产生的。     

纳米二氧化锆制备过程的DSC、TGA和XRD研究

用ＤＳＣ、ＴＧＡ和ＸＲＤ技术研究了在沉淀法制备纳米ＺｒＯ２的过程中，残留ＮＨ４Ｃｌ、ｐＨ值、滴加方式、以及结构稳定剂Ｙ２Ｏ３的添加量对结晶过程的影响。结果表明，残留ＮＨ４Ｃｌ使结晶化温度降低，使放热过程变为吸热过程。而ｐＨ值、滴加方式和结构稳定剂的添加对结晶过程无明显影响。     

Underpotential deposition of tin(II) on a gold disc electrode and determination of tin in a tin plate sample

This work describes a study of the underpotential deposition (UPD) of Sn²⁺ on a polycrystalline gold disc electrode using cyclic voltammetry (CV) and chronocoulometry (CC). Sn²⁺ ions showed well-defined peaks from UPD and UPD stripping (UPD-S) in 1 mol/L HCl solutions, while bulk deposition (BD) and BD stripping (BD-S) of the ions were also observed. The measured UPD shifts, E_UPD, between the UPD-S and the BD-S peaks were more than 200 mV. The UPD charge and the surface coverage of tin were measured by CC. A new method for determining Sn²⁺ was therefore developed, based on the excellent electrochemical properties of the Au/Sn UPD system. A plot of the UPD-DPASV (differential pulse anodic stripping voltammetry) signal versus the Sn(II) concentration was obtained for [Sn(II)] of 1.98×10^–7 to 3.64×10^–5 M. The method developed here has been applied to determine the tin in a tin plate sample.