Spherical Particles of Zirconia-Titania of Hexagonal Structure from a Neutral Amine Route

Through the sol–gel process, using the so-called neutral amine route, spherical particles of 1:1 zirconia–titania were synthesized from zirconium(IV) and titanium(IV) butoxides as well as 1,12-diaminododecane as precursor species. The obtained product exhibited a hexagonal structure, as determinated by X-ray diffraction data. The obtained material was also characterized by thermogravimetry, differential scanning calorimetry, infrared spectroscopy, scanning electron microscopy, and surface area measurements. Despite the release of template molecules on heating, the spherical morphology was retained up to about 1200°C, at which the disruption of the spheres took place.     

Effects of Adsorbed Polyaniline on Redox Process on MoO3 Surface

The effects exhibited by adsorbed conducting polyaniline on the redox process on a molybdenum oxide surface were studied. Thermogravimetric results indicate a 4% polyaniline deposition. Cyclic voltammograms of the adsorbed polymer on MoO3 show that polyaniline exerts remarkable effects on the molybdenum blue oxidation-reduction process, with oxidation and reduction potentials of 0.33 and 0.18 V, respectively. This effect strongly enhances the electrode response, and can be used as an important tool in qualitative and/or quantitative determinations of molybdenum in solution as well as in any substrate. Copyright 1999 Academic Press.     

Bis- through Tetrakis-Adducts of C60 by Reversible Tether-Directed Remote Functionalization and systematic investigation of the changes in fullerene properties as a function of degree,pattern, and nature of functionalization

By the tether-directed remote functionalization method, a series of bis- to hexakis-adducts of C₆₀, i.e., 1 – 7 (Fig. 1), had previously been prepared with high regioselectivity. An efficient method for the removal of the tether-reactive-group conjugate was now developed and its utility demonstrated in the regioselective synthesis of bis- to tetrakis(methano)fullerenes ( = di- to tetracyclopropafullerenes-C₆₀-I_h) 9 – 11 starting from 4, 5, and 7, respectively (Schemes 2, 4, and 5). This versatile protocol consists of a ¹O₂ ene reaction with the two cyclohexene rings in the starting materials, reduction of the formed mixture of isomeric allylic hydroperoxides to the corresponding alcohols, acid-promoted elimination of H₂O to cyclohexa-1,3-dienes, Diels-Alder addition of dimethyl acetylenedicarboxylate, retro-Diels-Alder addition, and, ultimately, transesterification. In the series 9 – 11 , all methano moieties are attached along an equatorial belt of the fullerene. Starting from C_2v-symmetrical tetrakis-adduct 15 , transesterification with dodecan-1-ol or octan-1-ol yielded the octaesters 16 and 17 , respectively, as noncrystalline fullerene derivatives (Scheme 3). The X-ray crystal structure of a CHCl₃ solvate of 11 (Fig. 3) showed that the residual conjugated π-chromophore of the C-sphere is reduced to two tetrabenzopyracylene substructures connected by four biphenyl-type bonds (Fig. 5). In the eight six-membered rings surrounding the two pyracylene (= cyclopent[fg]acenaphthylene) moieties, 6–6 and 6–5 bond-length alteration (0.05 Å) was reduced by ca. 0.01 Å as compared to the free C₆₀ skeleton (0.06 Å) (Fig. 4). The crystal packing (Fig. 6) revealed short contacts between Cl-atoms of the solvent molecule and sp²- and sp³-C-atoms of the C-sphere, as well as short contacts between Cl-atoms and O-atoms of the EtOOC groups attached to the methano moieties of 11 . The physical properties and chemical reactivity of compounds 1 - 11 were comprehensively investigated as a function of degree and pattern of addition and the nature of the addends. Methods applied to this study were UV/VIS (Figs. 7–11), IR, and NMR spectroscopy (Table 2), cyclic (CV) and steady-state (SSV) voltammetry (Table 1), calculations of the energies of the lowest uunoccupied mmolecular orbitals (LUMOs) and electron affinities (Figs. 12 and 13), and evaluation of chemical reactivity in competition experiments. It was found that the properties of the fullerene derivatives were not only affected by the degree and pattern of addition but also, in a remarkable way, by the nature of the addends (methano vs. but-2-ene-1, 4-diyl) anellated to the C-sphere. Attachment of multiple thano moieties along an equatorial belt as in the series 8 – 11 induces only a small perturbation of the original fullerene π-chromophore. In general, with increasing attenuation of the conjugated fullerene π-chromophore, the optical (HOMO-LUMO) gap in the UV/VIS spectrum is shifted to higher energy, the number of reversible one-electron reductions decreases, and the first reduction potential becomes increasingly negative, the computed LUMO energy increases and the electron affinity decreases, and the reactivity of the fullerene towards nucleophiles and carbenes and as dienophile in cycloadditions decreases.     

HL-2M 装置电子回旋共振加热及电流驱动系统设计与研制进展

根据 HL-2M 装置物理实验加热的需求,完成了总功率为 8MW 的电子回旋共振加热及电流驱动 (ECRH/ECCD)系统设计,开展了波源、传输及天线等关键部件研制。8MW ECRH/ECCD 系统,由 8 套 105GHz/  1MW/3s 波源系统、8 条内径为 63.5mm 的真空传输线及三套极向实时可控的发射天线构成。目前,已完成 ECRH/ECCD 系统关键部件研制及其相关的桌面与高功率性能测试。测试结果表明,微波源回旋管输出微波功率 达到1MW/3s,在真空度为 10^‒2Pa 的过模波纹圆波导传输线中能低耗稳定传输,发射天线极向全量程角度转动响 应时间在 50ms 以内。