Synthesis,characterization and electrocatalytic performance of a dinuclear triazenidosilver(I) complex for hydrogen production

Our group has developed a series of molecular electrocatalysts for hydrogen generation based on triazenido–metal complexes (cobalt, copper, etc.). In this paper, we first present the electrocatalytic performance of a new dinuclear silver complex, [Ag₂(L)₂], formed by the reaction of the triazenido ligand 1‐[(2‐carboxymethyl)benzene]‐3‐[(2‐methoxy)benzene]triazene (HL) with AgNO₃. At room temperature, the silver complex shows photoluminescence at 653 nm. The electrocatalytic systems based on this silver complex can afford 106.57 and 1536.36 moles of hydrogen per mole of catalyst per hour from acetic acid at an overpotential (OP) of 991.6 mV and from a neutral aqueous buffer (pH = 7.0) at an OP of 837.6 mV, respectively. Electrochemical investigations show that both silver ion and triazenido ligand play a role in determining the catalytic activities of the electrocatalytic system.     

Application of a dispersive micro‐solid‐phase extraction method for pre‐concentration and ultra‐trace determination of cadmium ions in water and biological samples

A method for the trace determination of cadmium ions in water, human urine and human blood serum samples using ultrasonic‐assisted dispersive micro‐solid‐phase extraction (UA‐D‐μSPE) was developed. Silica‐coated magnetic nanoparticles were coated with polythiophene, and the resulting sorbent was characterized using thermogravimetry, differential thermal analysis, scanning electron microscopy, Fourier transform infrared spectrometry and X‐ray diffraction. Following UA‐D‐μSPE, cadmium ions were quantified using graphite furnace atomic absorption spectrometry. A Box–Behnken design was used for optimization of important sorption and desorption parameters in UA‐D‐μSPE: in the sorption step, pH of solution, sorption amount and sonication time for sorption; in the desorption step, concentration of eluent, volume of eluent and sonication time. The optimum conditions for the method were: pH of solution, 7.5; sonication time for sorption, 3 min; sorption amount, 35 mg; type and concentration of eluent, HCl and 1.1 mol l^?1; volume of eluent, 360 μl; sonication time for desorption, 110 s. Under the optimized conditions the limit of detection and relative standard deviation for the detection of cadmium ions by UA‐D‐μSPE were found to be 0.8 ng l^?1 and <6%, respectively.     

Open‐cage fullerenes as tailor‐made container for a single water molecule

Water is the most important liquid on earth. Clusters of water have been investigated extensively in an effort to understand the bulk property of water. But the behavior of single water molecule without H‐bond has been rarely studied. Open‐cage [60]fullerenes have been shown to trap a single water molecule selectively over molecules with comparable size and act as the smallest “water bottle”. Copyright © 2013 John Wiley & Sons, Ltd.     

定-转子反应器在水脱氧工艺中的应用研究

在定-转子反应器中采用N₂-水脱氧、CO₂-水脱氧两个体系脱除水中的溶氧，考察了转子转速、液体体积流量以及气体体积流量对脱氧率和传质系数的影响，并对比了两个水脱氧体系的脱氧效果。实验结果表明：脱氧率随转子转速和气体体积流量的增加而升高，随液体体积流量的增加而降低；传质系数随着转子转速、液体体积流量、气体体积流量的增加而增加；此外，N₂-水脱氧体系的脱氧效果要优于CO₂-水脱氧体系。     

Chelating 2,2′-Diaminodiethylamine Cellulose Filters and X-ray Fluorescence for Preconcentration and Trace Analysis of Natural Waters

Abstract

The 2,2′-diaminodiethylamine (DEN) functional group can be expected to have ideal properties for the chelation of transition metals and their collection from aqueous solutions, independent of the alkali and alkaline earth ions concentration. Introducing DEN into cellulose filters allows straightforward preconcentration of trace cations by a simple filtration step, and the DEN-filter constitutes a suitable target for X-ray fluorescence (XRF) analysis. The linearity between the XRF-response on the loaded DEN-filter and the trace cation concentration in the solution appears excellent, up to a total filter capacity of ca. 3 μeq.cm^?2. The detection limits are around 0.5 μg. l^?1 in most practical cases. Accuracy and precision are around 10%. The applicability of the proposed procedure is illustrated on a comparative basis by XRF-analysis of drinking water and surface water, after preconcentration by DEN-filtration and by alternative procedures.     

Basic CuCO3/ligand as a new catalyst for 'on water' borylation of Michael acceptors,alkenes and alkynes: application to the efficient asymmetric synthesis of β‐alcohol type sitagliptin side chain

The efficient 'on water' β‐borylation using bis(pinacolato)diboron agent was achieved with a newly developed catalytic system based on basic copper carbonate and various ligands. The catalytic system was used for β‐borylation of various Michael acceptors, alkenes and alkynes. The presented methodology was successfully applied to the novel synthesis of β‐alcohol type sitagliptin side chain precursor via water‐based highly enantioselective β‐borylation followed by an oxidation process. Copyright © 2013 John Wiley & Sons, Ltd.     

Water‐soluble metalated and non‐metalated A2B‐ and A3‐corrole/amino acid conjugates: syntheses,characterization and properties

In this study, novel water‐soluble corrole amino acid conjugates were synthesized and characterized. The coupling reaction of A₂B‐ and A₃‐corroles with glycine ethyl ester and taurine under strong basic conditions proved to be successful and yielded di‐ and trifunctionalized corrole amino acid conjugates in good yields. The subsequent metalation of the corrole/amino acid conjugates broadens the scope for applications considerably. As examples, we herein show the catalytic activity of the Mn(III) A₃‐corrole towards O₂ evolution. First we employed tert‐butyl hydroperoxide (t‐BuOOH) as oxidant to obtain the Mn(V)oxo species and tetrabutyl ammonium hydroxide (TBAH) as hydroxide donor agent. Furthermore, the binding properties of the non‐metalated and the Mn(III) A₃‐corrole/amino sulfonic acid conjugates and transport of proteins were investigated and the conjugates exhibited binding to human serum albumin (HSA). Finally, a novel Ga(III) A₃‐corrole/amino sulfonic acid derivative was synthesized and we briefly describe the photophysical properties of this compound. Copyright © 2013 John Wiley & Sons, Ltd.     

义马煤田煤矿水害规律与防治技术

为了掌握义马煤田水害规律以正确指导煤矿的防治水工作,分析研究了历次突水资料、地质构造、小煤矿分布、河流流经区域、主要含水层和隔水层、采煤厚度及采后导水裂隙发育情况等,指出:随着小煤矿的关闭、河道疏浚、浅部地裂缝充填和大矿采掘活动向深部转移,矿井主要水害由大气降水、地表河水和小窑水转化为顶板水;顶板水威胁主要在义马向斜的核部、采深大于700 m的区域,断层尖灭端和断层带富水性较强,顶板突水及其强度与采厚、周期来压关系密切。针对顶板水害,提出了采用"三图—双预测法"对顶板突水的水源、通道和强度做出预测和评价;采用井上下物探方法,圈出顶板疑似富水区,并进行采前预疏放;完善工作面排水系统,提高抗水灾能力等防治水技术。     

Study of Ganga River – Groundwater Interaction Using Environmental Oxygen-18

The influent and effluent characteristics of river Ganga in the Hardwar-Narora sector in Uttar Pradesh, India was studied using environmental oxygen-18. δ¹⁸O of river water and also of groundwater close to the river course was monitored at 8 stations along the 220 km stretch for a period of ten months. δ¹⁸O of the river during the monsoon months (June to September) was about – 10 at all the stations. However, during the dry months from October to April, the δ¹⁸O of the river was enriched progressively from Hardwar to Narora. The enrichment indicated groundwater contribution to the river during the non-monsoon months. The contribution was comuted using the principle of isotope balance.