Spectroscopic study of BixEu1−xVO4 and BiyGd1−yVO4 mixed oxides

The mixed oxides Bi_xEu_1−xVO₄ and Bi_yGd_1−yVO₄ crystallize in a zircon-type structure, for 0 <x < 0.6 and 0 < y < 0.64, and in a fergusonite-type structure, for 0.94 < x < 1 and 0.93 < y < 1. A process of competition between the dominant and the constrained effects of the lone-pair 6s² of Bi³⁺ is discussed. The diffuse reflectance spectroscopic studies of these mixed oxides are presented. The observed broad bands are attributed to charge transfer processes and the sharp peaks in the Bi_xEu_1−xVO₄ spectra are ascribed to intra-configurational 4f – 4ftransitions of the Eu³⁺ ion. The broad absorption shift in BiLnVO₄ (Ln : Eu and Gd) compounds to the longer wavelengths range, when Bi is introduced in the LnVO₄ lattice, is ascribed to charge transfer processes in a Bi-VO₄ center and are interpreted assuming a Jahn-Teller effect in the excited state of Bi³⁺. The concept of an internal pressure of Bi³⁺ ions is also used to explain the broad A-band shifts.     

掺铝高性能镍电极研究

掺铝的Ni(OH)2 通过共沉淀法制备,X射线粉末衍射法测定其晶体结构为α型层状结构. 用循环伏安法和恒流充放电法研究其电化学性能,实验结果表明掺铝镍电极具有比普通镍电极高得多的充放电容量,放电电位高80 m V.     

Charge transfer in the collision system He<Superscript>2+</Superscript> + C<Stack><Subscript>60</Subscript><Superscript>+</Superscript></Stack>: Theory and experiment

Fullerenes are a direct link between atoms with discrete electronic energy levels and solids with a band structure and a well-defined surface. In this paper, we report on a quantum mechanical treatment of charge transfer and ionization in the ion-ion collision system ³He²⁺ + C ₆₀ ⁺ . This approach considers under- and over-barrier transitions through the one-dimensional barrier between the collision partners. The calculated cross sections for charge transfer compare favorably with experimental data measured in the center-of-mass energy range from 27 to 196 keV employing the crossed beams technique.     

压力膨化处理对正极性聚丙烯蜂窝膜的驻极体性质的影响

压力膨化处理工艺能够显著改善聚丙烯蜂窝薄膜（cellular polypropylene） 驻极体的压 电活性.通过热脉冲技术、表面电位衰减测量及TSD 电流谱分析等研究了经恒压正电晕充电 的聚丙烯蜂窝膜的陷阱能级分布特征，讨论了压力膨化处理工艺对这类蜂窝膜驻极体电荷稳 定性及电荷输运特性的影响.结果说明，PP 蜂窝膜内存在着位于中能级区的能值各异的三种 分立陷阱，深能值陷阱和浅能值陷阱的大多数位于孔洞膜近表面的体层或体内，而中等能值 陷阱则主要位于自由面附近.压力膨化处理改变了PP 蜂窝膜的能阱状态并在一定程度上降低 了这类孔洞膜驻极体的电荷储存稳定性，但没有明显影响其由慢再俘获效应占主导地位的脱 阱电荷输运特性. 关键词： 压力膨化处理 聚丙烯蜂窝膜 驻极体 电荷储存与陷阱分布 电荷输运     

Field‐effect transistors based on PPV derivatives as a semiconducting layer

A series of modified thiophene groups containing PPV‐based semiconducting materials, poly[(2,5‐bis(octyloxy)‐1,4‐phenylenevinylene)‐alt‐(2,2′bithienylenevinylene)] ( PPBT ), poly[(2,5‐bis(octyloxy)‐1,4‐phenylenevinylene)‐alt‐(5,5‐thiostilylenevinylene)] ( PPTVT ), have been synthesized through a Horner coupling reaction. From the FTIR and ¹H NMR spectroscopy, the configuration of the vinylene groups in the polymers was all trans (E) geometry. The weight‐average molecular weights (M_w) of PPBT and PPTVT were found to be 11,700 and 11,800, with polydispersity indices of 2.51 and 2.53, respectively. PPBT and PPTVT thin films exhibit UV–visible absorption maxima at 538 and 558 nm, respectively, and the strong absorption shoulder peaks at 578 and 602 nm, respectively. Solution processed field‐effect transistors (FET) fabricated using all the polymers showed p‐type OTFT characteristics. The field‐effect mobility of the PPTVT was obtained up to 2.3 × 10^?3 cm² V^?1 s^?1, an on/off ratio of 1.0 × 10⁵ with ambient air stability. Studies of the atomic force microscopy (AFM) and X‐ray diffraction (XRD) analysis of the polymer thin films revealed that all the polymers were amorphous structure. The greater planarity and rigidity of PPTVT compared to PPBT results in elongation of conjugation length and better π–π stacking of polymer chains in amorphous region, which leads to improved FET performance. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 111–120, 2009     

Studies on drug–DNA complexes,adriamycin–d‐(TGATCA)2 and 4′‐epiadriamycin–d‐(CGATCG)2, by phosphorus‐31 nuclear magnetic resonance spectroscopy

The complexes of adriamycin–d‐(TGATCA)₂ and 4′‐epiadriamycin–d‐(CGATCG)₂ are studied by one‐ and two‐dimensional ³¹P nuclear magnetic resonance spectroscopy (NMR) at 500 MHz in the temperature range 275–328 K and as a function of drug to DNA ratio (0.0–2.0). The binding of drug to DNA is clearly evident in ³¹P? ³¹P exchange NOESY spectra that shows two sets of resonances in slow chemical exchange. The phosphate resonances at the intercalating steps, T1pG2/C1pG2 and C5pA6/C5pG6, shift downfield up to 1.7 ppm and that at the adjacent step shift downfield up to 0.7 ppm, whereas the central phosphate A3pT4 is relatively unaffected. The variations of chemical shift with drug to DNA ratio and temperature as well as linewidths are different in each of the two complexes. These observations reflect change in population of B_I/B_II conformation, stretching of backbone torsional angle ζ, and distortions in O? P? O bond angles that occur on binding of drug to DNA. To the best of our knowledge, there are no solution studies on 4′‐epiadriamycin, a better tolerated drug, and binding of daunomycin or its analogue to d‐(TGATCA)₂ hexamer sequence. The studies report the use of ³¹P NMR as a tool to differentiate various complexes. The specific differences may well be the reasons that are responsible for different antitumor action of these drugs due to different binding ability and distortions in DNA. Copyright © 2009 John Wiley & Sons, Ltd.     

Redox Potential and Crystal Chemistry of Hexanuclear Cluster Compounds

Most of TM₆-cluster compounds (TM = transition metal) are soluble in polar solvents, in which the cluster units commonly remain intact, preserving the same atomic arrangement as in solids. Consequently, the redox potential is often used to characterize structural and electronic features of respective solids. Although a high lability and variety of ligands allow for tuning of redox potential and of the related spectroscopic properties in wide ranges, the mechanism of this tuning is still unclear. Crystal chemistry approach was applied for the first time to clarify this mechanism. It was shown that there are two factors affecting redox potential of a given metal couple: Lever’s electrochemical parameters of the ligands and the effective ionic charge of TM, which in cluster compounds differs effectively from the formal value due to the bond strains around TM atoms. Calculations of the effective ionic charge of TMs were performed in the framework of bond valence model, which relates the valence of a bond to its length by simple Pauling relationship. It was also shown that due to the bond strains the charge depends mainly on the atomic size of the inner ligands.     

New paradigms for synthetic pathways inspired by bioorganometallic chemistry

Two series of particular examples of reactions used in bioorganometallic chemistry are described. One based on a decomplexation-complexation reaction, indicates how, starting from a cymantrenyl derivative, a range of organometallic complexes bearing various metals can be prepared. The second one refers to the easy synthesis in water of the very versatile Alberto's reagent, which leads to new organometallic radiopharmaceuticals of Tc and Re.