Übergangsmetall-Carben-Komplexe,CXXXVII Darstellung zweikerniger Gold(I)-Biscarben-Komplexe durch Carbenübertragungen von Wolfram auf Gold

The binuclear tungsten(0) biscarbene complexes3 and4 react with tetrachloroauric acid (stöchiometric ratio 1 : 2) to give the corresponding gold(I) complexes5 and6 involving the transfer of biscarbene ligands from two tungsten to two gold fragments. Preparation and spectroscopic data are described.

Herrn Prof. Dr.K. Schlögl zum 60. Geburtstag gewidmet.     

Potentiometric determination of silver(I), palladium(II) and gold(III) in mixtures by use of an iodide-selective electrode

Two procedures are proposed for the potentiometric determination of Ag(I), Pd(II) and Au(III) in binary mixtures, by titration with potassium iodide solution, and use of a commercial iodide electrode as sensor. In the first procedure, two aliquots of the mixture are titrated, at pH 2.0 ± 0.2 and 9.0 ± 0.2, adjusted with dilute sulphuric acid and ammonia solution. At pH 2.0, the titrant reacts with both metals, whereas at pH 9.0, Ag(I) is the only reactant. The second procedure utilizes titration of two aliquots of the mixture in the presence and absence of a selective masking agent. The methods have been applied to the determination of these metals in some jewellery alloys.     

微乳法制备Au／Fe2O3水煤气变换反应催化剂 Ⅰ．制备参数对催化剂活性的影响

 分别在TritonX－100／正己醇／环己烷／水和十六烷基三甲基溴化铵（CTAB）／正己醇／水的W／O型微乳液体系中合成了Au／Fe2O3催化剂，考察了主要制备参数对催化剂水煤气变换活性的影响．结果表明，催化剂的焙烧温度、水与表面活性剂的质量比（rw）、表面活性剂浓度（W）、表面活性剂种类及催化剂活性组分金的负载量均对催化剂活性有显著的影响．催化剂的最佳焙烧温度为250℃，催化活性随着rw和W的增加而降低，由TritonX－100制得的催化剂的活性高于由CTAB制得的催化剂．当金负载量为3％，水煤气变换反应温度为200℃时，CO的转化率可达99．5％．     

基于静电吸附甲苯胺蓝和纳米金固定过氧化物酶生物传感器的研究

以玻碳电极为基底,电聚合邻氨基苯甲酸(ABA),使其形成带负电的界面,通过分子间静电作用力,自组装一层带正电荷的电子媒介体甲苯胺蓝(TB),再通过媒介体的氨基吸附纳米金,最后静电吸附固定辣根过氧化物酶制备出H2O2传感器。探讨了膜聚合时间、媒介体组装时间、pH、温度、工作电位对电极响应的影响。在优化的实验条件下,该传感器对H2O2电流响应与其浓度为1.5×10-5~1.3×10-3mol/L范围内呈线性关系;检出限为5.6×10-6mol/L。此外,该传感器具有较低的工作电位,能有效地消除抗坏血酸等的干扰。     

pH值对硫醇修饰的金纳米粒子聚集态的影响

制备了3 巯基丙酸修饰的金纳米颗粒,溶胶的pH值变化导致颗粒表面的电荷发生变化.随着pH值的降低,颗粒的聚集体增大,在pH值小于4时颗粒下沉.加碱增大溶胶的pH值,聚集的颗粒会重新分散.     

Early–Late Heterometallic Complexes of Gold and Zirconium: Photoluminescence and Reactivity

OH functionalized triarylphosphines were used to assemble zirconocene‐based metalloligands with phosphine donor sites in varying positions. These complexes were subsequently treated with different gold precursors to obtain early–late heterometallic compounds in which the metal atoms exhibit different intermetallic distances. All compounds were fully investigated by spectroscopic techniques, photoluminescence measurements and single crystal X‐ray diffraction. Quantum chemical calculations were also performed. Some compounds show bright emission even at room temperature with quantum yields of up to 19 % (excitation at 350 nm). Furthermore, the reactivity of dimethyl zirconocene derivatives towards gold complexes was investigated, revealing simultaneous ligand exchange and transmetallation reactions.     

Experimental and Theoretical Study of the Reactivity of Gold Nanoparticles Towards Benzimidazole‐2‐ylidene Ligands

The reactivity of benzimidazol‐2‐ylidenes with respect to gold nanoparticles (AuNPs) has been investigated using a combined experimental and computational approach. First, the grafting of benzimidazol‐2‐ylidenes bearing benzyl groups on the nitrogen atoms is described, and comparisons are made with structurally similar N‐heterocyclic carbenes (NHCs) bearing other N‐groups. Similar reactivity was observed for all NHCs, with 1) the erosion of the AuNPs under the effect of the NHC and 2) the formation of bis(NHC) gold complexes. DFT calculations were performed to investigate the modes of grafting of such ligands, to determine adsorption energies, and to rationalize the spectroscopic data. Two types of computational models were developed to describe the grafting onto large or small AuNPs, with either periodic or cluster‐type DFT calculations. Calculations of NMR parameters were performed on some of these models, and discussed in light of the experimental data.     

Nanosecond Time‐Resolution Study of Gold Nanorod Rotation at the Liquid–Solid Interface

Early studies showed that the adsorption of nanorods may start from a special “anchored” state, in which the nanorods lose translational motion but retain rotational freedom. Insight into how the anchored nanorods rotate should provide additional dimensions for understanding particle–surface interactions. Based on conventional time‐resolution studies, gold nanorods are thought to continuously rotate following initial interactions with negatively charged glass surfaces. However, this nanosecond time‐resolution study reveals that the apparent continuous rotation actually consists of numerous fast, intermittent rotations or transitions between a small number of weakly immobilized states, with the particle resting in the immobilized states most of the time. The actual rotation from one immobilized state to the other happens on a 1 ms timescale, that is, approximately 50 times slower than in the bulk solution.