Organoselenido Complexes of Tungsten

Organometallic tungsten selenido complexes of the type [cpW(CO)₃]₂Se_m; m = 2 (1), 3 (2), 4 (3), can be easily synthesized via insertion of selenium into the alkali-metal tungsten bond of LiWcp(CO)₃ in appropriate ratios and subsequent oxidation of the produced W-selenolates with O₂/SiO₂. In contrast, reactions of K₂Se₆ with [cpW(CO)₃Cl] and 18-crown-6 in DMF lead to a mixture óf [cpW(CO)₃]₂Se₄ (3), the η¹ Se-bonded selenocarbamato complex [cpW(CO)₃SeC(O)NMe₂] (4) and the ionic complex [(18-crown-6)K]⁺[cpW(Se₄)₂]^? (5). The crystal structures of 3 and 4 together with their ⁷⁷Se NMR data are presented.     

Li原子掺杂C28单分子器件的热自旋输运性质

利用第一性原理对Li原子掺杂C₂₈的分子器件的热自旋输运性质进行了计算。在不同的温度场下,上下自旋分别为Li原子掺杂C₂₈的分子器件中的空穴和电子提供了输运通道,在MJ₁和MJ₃分子器件中,热自旋电流随着温度增加而增大,但在MJ₂分子器件中,热自旋电流先增大再减小。三种分子器件都出现了自旋塞贝克效应,MJ₂还出现了负微分电阻现象,利用费米-狄拉克分布和自旋输运谱对其物理机理进行了解释。根据Li掺杂C₂₈的单分子器件的热自旋输运性质,可设计新的自旋纳米器件。     

Physical- and Bio-Organic Chemstry of Nonbonded Selenium· · ·Oxygen Interactions

Weak nonbonded interaction between a divalent selenium and an oxygen atom (i.e., Se···O interaction) frequently plays important roles in chemical and biological functions of selenium compounds. To establish that ⁷⁷ Se NMR is an easy experimental probe to diagnose the strength of an Se···O interaction, 3 series of 2-substituted benzeneselenenyl derivatives, which have an intramolecular Se···O interaction in solution, were employed. By comparing the ⁷⁷ Se NMR chemical shifts (δ _Se ) with those observed for other series of selenium compounds, which have an intramolecular Se···Y (Y = N, O, F, Cl, or Br) interaction, approximate linear correlation was found between the δ _Se values and the strengths of the nonbonded Se···Y interactions evaluated by natural bond orbital analysis at the B3LYP level. The correlation will be useful for estimating the strength of an Se···O interaction simply from the ⁷⁷ Se NMR chemical shift. By extending the chemistry of nonbonded Se···O interactions to structural biology, analogous S···O interactions have been discovered in protein architecture. The directional features were, however, different from those of Se···O and S···O interactions of small organic compounds.     

Electrochemical Oxidation of Ibuprofen and Its Voltammetric Determination at a Boron‐Doped Diamond Electrode

The electrochemical oxidation of ibuprofen at a boron‐doped diamond electrode (BDDE) and its voltammetric determination is reported for the first time. A well‐defined oxidation peak was observed at around 1.6 V in 0.1 mol L^?1 H₂SO₄ solution with 10 % (v/v) ethanol at the BDDE surface activated by either cathodic or anodic pretreatments. A differential‐pulse voltammetric method for the determination of ibuprofen in pharmaceutical formulations was optimized with a detection limit of 5 µmol L^?1 and compared with the British Pharmacopeia method.     

Ultra‐low friction of fluorine‐doped hydrogenated carbon film with curved graphitic structure

Fluorine‐doped hydrogenated carbon film was grown by chemical vapor deposition technique using CH₄ and CF₄ as feedstock, with a pulse DC‐bias power supply. The structure of as‐deposited film was characterized by transmission electron microscopy and Raman spectra. The results suggested that the film could be considered as composite thin film with curved graphitic structures embedded in amorphous carbon matrix. The mechanical properties and friction coefficient were tested by TI 950 TriboIndenter and UMT‐2 at humidity of 30%, respectively. The results showed that the film exhibited high hardness (~11.04 GPa), good elasticity recovery(~83%) and ultra‐low coefficient of friction (~0.01). Copyright © 2013 John Wiley & Sons, Ltd.     

Bioconjugated Luminescent Nanoparticles for Biological Applications

Abstract

Inorganic nanostructures that interface with biological systems have recently attracted widespread interest in biology and medicine. Nanoparticles are thought to have potential as novel luminescent probes for both diagnostic (e.g., imaging) and therapeutic (e.g., drug delivery) purposes because of their size comparable to biomolecules and their novel optical, electronic, and magnetic properties. Critical issues for successful nanoparticle delivery include the ability to target specific tissues and cell types and escape from the biological particulate filter known as reticuloendothelial system. Three distinct types of luminescent nanoparticles have been identified which show promise in bioanalysis, namely dye‐doped nanoparticles, semiconductor and metal nanoparticles. In this article we examine the recent advances in the development of dye‐doped nanoparticles, metal and semiconductor nanoparticles, bioconjugation schemes to attach these nanoparticles to biomolecules and a few biological applications.     

Preparation and Characterization of Nanocrystalline Fe-Doped TiO2 Film on Different Substrates and Its Application in Degrading Dyeing Water

TiO₂ and Fe-doped TiO₂ thin films were prepared on the substrates (glass plates and glass microballs) after dipped in colloid and calcined at 500°C. The films have been characterized by UV-absorption, x-ray diffraction and atomic force microscopy (AFM). The investigated Fe-doped TiO₂ (A nominal 10 wt% Fe₂O₃ was impregnated) thin films were obtained by sol-gel method. The characterization results suggest that the calcined thin films primarily consist of TiO₂ anatase. And the light absorption curve of the TiO₂ films modified with Fe showed that red shift had happened by the dope of Fe. TiO₂/beads as photocatalyst were used to degrade the simulated dyeing water which contains reactive deep-blue dye (K-R). Through the degradation experiment, we found that the dope of Fe promoted the photocatalytic activities. The results showed that the dyeing water can be decomposed more effectively by the photocatalytic oxidation of Fe/TiO₂ film on glass micro-balls than glass plates.     

Anodic stripping voltammetry of antimony at unmodified carbon electrodes

Antimony is an element of significant environmental concern, yet has been neglected relative to other heavy metals in electroanalysis. As such very little research has been reported on the electroanalytical determination of antimony at unmodified carbon electrodes. In this paper we report the electrochemical determination of Sb(III) in HCl solutions using unmodified carbon substrates, with focus on non-classical carbon materials namely edge plane pyrolytic graphite (EPPG), boron doped diamond (BDD) and screen-printed electrodes (SPE). Using differential pulse anodic stripping voltammetry, EPPG was found to give a considerably greater response towards antimony than other unmodified carbon electrodes, allowing highly linear ranges in nanomolar concentrations and a detection limit of 3.9?nM in 0.25?M HCl. Furthermore, the sensitivity of the response from EPPG was 100 times greater than for glassy carbon (GC). Unmodified GC gave a comparable response to previous results using the bare substrate, and BDD gave an improved, yet still very high limit of detection of 320?nM compared to previous analysis using an iridium oxide modified BDD electrode. SPEs gave a very poor response to antimony, even at high concentrations, observing no linearity from standard additions, as well as a major interference from the ink intrinsic to the working electrode carbon material. Owing to its superior performance relative to other carbon electrodes, the EPPG electrode was subjected to further analytical testing with antimony. The response of the electrode for a 40?nM concentration of Sb(III) was reproducible with a mean peak current of 1.07?µA and variation of 8.4% (n?=?8). The effect of metals copper, bismuth and arsenic were investigated at the electrode, as they are common interferences for stripping analysis of antimony.     

Li+掺杂对Y2SiO5:Pr3+上转换发光性能影响

采用溶胶-凝胶法制备Li+掺杂改性的Y2SiO5:Pr3+上转换发光材料,考察了Li+掺杂对样品晶型及发光性能的影响。采用XRD,DSC-TGA,FS对所制备的材料进行表征,结果表明Li+掺入浓度在7%～8%(摩尔分数)之间会引起Y2SiO5晶体类型由X1型转变为X2型,且Li+掺入后样品转晶型温度由950℃降至800℃;样品经800℃煅烧处理后以X1型Y2SiO5为主相,850℃煅烧处理后以X2型Y2SiO5为主相;Li+掺入同时会提高Y2SiO5:Pr3+材料的上转换发光强度,Li+最佳掺杂浓度为10%,对于双掺杂Pr3+,Li+:Y2SiO5体系中Pr3+最佳掺杂浓度为1.2%。     

Ag-Ag2Se共敏化ZnO花-棒异质结构的合成及其光电化学特性

采用水相法合成ZnO花-棒(ZFRs)有序阵列结构,同时利用离子交换法,制备Ag和Ag₂Se量子点共敏化光ZnO光阳极(AA-ZFRs)。通过扫描电子显微镜(SEM)、X射线粉末衍射(XRD)、X射线能量色散谱(EDS)和透射电子显微镜(TEM)等手段对样品进行了分析和表征,并测试其光电化学特性以及量子效应。结果表明,Ag-Ag₂Se共敏化ZnO花-棒三维有序结构对太阳光的吸收范围延展至近红外区(750 nm),并且在敏化层与ZnO基质界面形成异质结,有效的抑制光生电子-空穴对复合,增强光转换量子效应,从而提高光电化学性能,开路电压达到-0.77 V,短路电流为0.64 mA。