The Enrichment of Stale Tailings of Bom-gorhon Tungsten Ore Deposits

The results of mineralogical studies of technogenic tungsten raw material (stale tailings of Bom-Gorhon deposit) are represented. Its particle size distribution as well as tungsten and accompanying element distribution among the fractions were determined. The necessity of grinding the heaps down to 0.2-0.25 mm in size was established. It allows increasing the recovery rate of two or more times in comparison with the traditional pattern of tailing processing.     

云南普朗超大型斑岩铜矿特征及成矿模型

普朗斑岩铜矿床位于义敦岛弧带南端,是中国目前可以确定的印支期斑岩铜矿床的典型代表.矿床产于由石英闪长玢岩、石英二长斑岩小岩株组成的复式岩体中,通过野外观察和典型地质体的辉钼矿Re-Os年龄、黑云母Ar/Ar年龄和K-Ar年龄测定,确定成矿年龄为(213±3.8)～(216.0±1) Ma,为晚三叠世诺利期,表明普朗斑岩铜矿床的成矿作用在印支期完成.含矿岩体蚀变分带明显,由中心向外发育强硅化带(局部)→钾长石、黑云母化带→石英、绢云母化带→青磐岩化带(局部发育伊利石-碳酸岩化带).工业矿体主要产于石英二长斑岩中的钾长石、黑云母化带和石英、绢云母化带.矿床具有斑岩铜矿中下部细粒状浸染、中上部细网脉状浸染和顶部围岩中产出大脉状矿体的"三层楼"模式.其斑岩体、元素组合及矿化特征与蒙古的欧玉·陶勒盖斑岩铜矿可以对比,资源潜力巨大.     

Accumulation of endogenous and exogenous nucleic acids in “Touch DNA” components on hands

Successful forensic DNA profiling from handled items is increasingly routine in casework. This “touch DNA” is thought to contain both cellular and acellular nucleic acid sources. However, there is little clarity on the origins or characteristics of this material. The cellular component consists of anucleate, terminally differentiated corneocytes (assumed to lack DNA), and the occasional nucleated cell. The acellular DNA source is fragmentary, presumably cell breakdown products. This study examines the relative contributions each component makes to the hand-secretions (endogenous) and hand-accumulations (exogenous) by recovering rinses from the inside and outside of worn gloves. Additionally, cellular and acellular DNA was measured at timepoints up to 2 h after hand washing, both with and without interim contact. Microscopic examination confirmed cell morphology and presence of nucleic acids. Following the novel application of a hair keratinocyte lysis method and plasma-DNA fragment purification to hand rinse samples, DNA profiles were generated from both fractions. Exogenous cell-free DNA is shown to be a significant source of touch DNA, which reaccumulates quickly, although its amplifiable nuclear alleles are limited. Endogenous DNA is mostly cellular in origin and provides more allelic information consistently over time.     

Experimental and four‐component relativistic DFT studies of tungsten carbonyl complexes

We present a theoretical and experimental study of the structure and nuclear magnetic resonance (NMR) parameters of the pentacarbonyltungsten complexes of η¹‐2‐(trimethylstannyl)‐4,5‐dimethylphosphinine, η²‐norbornene, and imidazolidine‐2‐thione. The three complexes have a pseudo‐octahedral molecular structure with the six ligands bonded to the tungsten atom. The η¹‐2‐(trimethylstannyl)‐4,5‐dimethylphosphinine‐pentacarbonyl tungsten complex was synthesized for the first time. For all compounds, we present four‐component relativistic calculations of the NMR parameters at the Dirac–Kohn–Sham density functional level of theory using hybrid functionals. These large‐scale relativistic calculations of NMR chemical shifts and spin–spin coupling constants were compared with available experimental data, either taken from the literature or measured in this work. The inclusion of solvent effects modeled using a conductor‐like screening model was found to improve agreement between the calculated and experimental NMR parameters, and our best estimates for the NMR parameters are generally in good agreement with available experimental results. The present work demonstrates that four‐component relativistic theory has reached a level of maturity that makes it a convenient and accurate tool for modeling and understanding chemical shifts and indirect spin–spin coupling constants of organometallic compounds containing heavy elements, for which conventional non‐relativistic theory breaks down. Copyright © 2015 John Wiley & Sons, Ltd.     

Gold Carbenoids: Lessons Learnt from a Transmetalation Approach

Carbophilic catalysts that are based on Au^I allow a host of different nucleophiles to be added across various π systems. 1 – 3 Although many of these reactions are thought to proceed via gold carbenoids, the challenge to observe and characterize these putative intermediates has basically been unmet. 4 The current mechanistic interpretation therefore largely relies on indirect evidence and computational data, some of which are subject to debate. 5 In an attempt to fill this gap, we pursued a potential route to gold carbenoids by formal transmetalation of chromium or tungsten Fischer carbene complexes with [LAu]⁺. Whereas this transformation proceeds with exceptional ease as long as a stabilizing heteroelement is present on the carbene center, it stops half‐way in its absence. Rather unusual bimetallic arrays are formed, which allow the charge density to delocalize over several positions. The obvious difficulty of releasing an “unstabilized” gold carbenoid has potential mechanistic implications for the understanding of π‐acid catalysis in general.     

A Convenient Photocatalytic Fluorination of Unactivated CH Bonds

Fluorination reactions are essential to modern medicinal chemistry, thus providing a means to block site‐selective metabolic degradation of drugs and access radiotracers for positron emission tomography imaging. Despite current sophistication in fluorination reagents and processes, the fluorination of unactivated C? H bonds remains a significant challenge. Reported herein is a convenient and economic process for direct fluorination of unactivated C? H bonds that exploits the hydrogen abstracting ability of a decatungstate photocatalyst in combination with the mild fluorine atom transfer reagent N‐fluorobenzenesulfonimide. This operationally straightforward reaction provides direct access to a wide range of fluorinated organic molecules, including structurally complex natural products, acyl fluorides, and fluorinated amino acid derivatives.     

Tungsten‐Catalyzed Regio‐ and Enantioselective Aminolysis of trans‐2,3‐Epoxy Alcohols: An Entry to Virtually Enantiopure Amino Alcohols

The first catalytic enantioselective aminolysis of trans‐2,3‐epoxy alcohols has been accomplished. This stereospecific ring‐opening process was efficiently promoted by a tungsten/bis(hydroxamic acid) catalytic system, furnishing various anti‐3‐amino‐1,2‐diols with excellent regiocontrol and high enantioselectivities (up to 95 % ee). Moreover, virtually enantiopure 3‐amino‐1,2‐diols could be obtained by the sequential combination of two reactions that both involve the use of a chiral catalyst.     

镍修饰WO3膜光电化学氧化水的研究

在强碱性溶液中低电压低电流条件下在W基底上经阳极氧化得到致密WO3层,而后在酸性条件下在WO3表面经光辅助电化学还原沉积镍,所获得的复合电极具有优异的光电化学氧化水的活性和稳定性.SEM,EDX,XPS和TEM等表征表明复合电极中具有体心立方结构的W基底经阳极氧化形成了具有单斜结构的WO3层,表面修饰的镍物种以Ni(OH)2形式存在.光电化学实验表明WO3层对可见光具有良好的光响应,表面修饰镍后,光电氧化水的起始电位显著降低,电极的稳定性也得以提高.     

Synergistic effect of W and P on ZSM-5 and its catalytic performance in the cracking of heavy oil

In order to develop the conversion of heavy oil with a high yield of propylene in the catalytic cracking process, ZSM-5 zeolite was modified by tungsten and phosphorus, which was proved to be an effective method. Characterization results show that the improvement of catalytic performance could be correlated to the interaction of phosphorus and tungsten species on ZSM-5. P inhibited the aggregation of tungsten species on ZSM-5 and was conductive to convert the tungsten species with octahedral coordination into tetrahedral coordination. And this ultimately led to that more acid sites were reserved after hydrothermal treatment in the tungsten and phosphorus co-modified ZSM-5 catalyst. Phosphorus species played an important role to restrain the dehydrogenation activity of tungsten. In addition, a model reflecting the interaction between tungsten species and ZSM-5 framework was proposed.     

Electrochemical codeposited polypyrrole–tungsten oxide composite materials with wide potential windows

The three-dimensional morphology has sufficient interface contact and can be in favor of the electronic transport process. In this work, the demand for high-performance electrodes such as energy storage devices has been designed. Polypyrrole and tungsten oxide composite materials (PPy-WO₃) have been synthesized by cyclic voltammetry (CV) technology at −0.6 to 0.9 V versus saturated calomel electrode (SCE) for 20 cycles. The PPy-WO₃^{20 mV/s}, PPy-WO₃^{60 mV/s}, and PPy-WO₃^{120 mV/s} electrodes have been prepared by CV technology at sweep rates of 20, 60, and 120 mV/s. The influences of scan rate on morphologies and charge storage properties of the composites are discussed. Among them, a three-dimensional flake structure for PPy-WO₃^{20 mV/s} with a size of up to several micrometers was synthesized. PPy-WO₃^{20 mV/s} composites as electrode materials exhibit a wide charge storage potential window of 1.4 V (between −0.9 and 0.5 V vs. SCE) and a specific capacitance of 145.13 F/g at 1 mA/cm². Moreover, the long-term stability of PPy-WO₃^{20 mV/s} and PPy has been investigated in 5 M LiCl aqueous electrolyte. The stability of the materials can be improved by inorganic and organic composites.