La(1-x)Pr_xP_5O_(14)晶体的研究

用水热法研究了La12xPr xP5O14(LaPrPP)(0 < x < 1,原子百分含量)晶体的生长,测定了La0.2Pr0.8PP晶体结构为 单斜晶系,空间群为P21/c。晶体的密度为3.27g/cm3,分解温度为915℃。分析了室温下晶体在紫外、可见区的吸 收、荧光和红外光谱,利用Judd2Ofeld 理论计算了PrPP 和La0. 2Pr0. 8PP 晶体中Pr3 + 的实验振子强度,得到一些规律性结果,观察到Pr3 + 的3 P0 —3 H6 跃迁的红色发射很强。

Gas-phase ion - Molecule reactions of neutral C-60 with the plasmas of alkyl methyl ethers and primary alcohols

The gas-phase ion-molecule reactions of C-60 with the methoxymethyl ion [CH3O=CH2](+) and the 1-hydroxyethyl ion [CH3CH=OH](+) generated under the self-chemical-ionization (self-CI) conditions of alkyl methyl ethers and primary alcohols were studied in the ion source of a mass spectrometer. The adduct ions [C60C2H5O](+) and protonated molecules [C60H](+) were observed as the major products of C-60 with the plasma of alkyl methyl ethers. On the contrary, the reactions of C-60 With the plasmas of primary alcohols produced few corresponding adduct ions. The AM1 semiempirical molecular orbital calculations were carried out on 14 possible structures. The calculated results showed that the most stable structure among the possible isomers of [C60C2H5O](+) is the [3+2] cycloadduct. According to experimental and theoretical results, the pathway for the formation of the adduct was presented.

H_8[P_4W_(14)O_(58)Na_4(H_2O)_(20)]·16H_2O的合成、晶体结构与性质

用水热法合成了 H8[P4 W14 O58Na4 (H2 O) 2 0 ]· 16 H2 O,通过 X射线单晶衍射、元素分析和IR进行了结构表征 ,用 TG- DTA研究了热稳定性 .晶体属三斜晶系 ,P1空间群 ,a=1.1379(2 )nm,b=1.36 32 (3) nm,c=1.6 2 71(3) nm;α=78.2 0 (3)°,β=71.2 0 (3)°,γ=71.6 2 (3)°;V=2 .2 52 5(8) nm3 ,Z=1,Mr=4 374 .38,Dc=3.2 2 5mg/ cm3 ,μ=18.0 0 7mm-1,F(0 0 0 ) =1972 ,R=0 .0 74 2 ,Rw=0 .2 0 0 4 .标题化合物的阴离子是由两个 PW7O2 9Na2 (H2 O) 10 亚单元通过与两个磷原子上键合的氧连接而成 ,分子内形成了一个 0 .6 6 14nm× 0 .3189nm的微孔.

Electrochemical probe of hydroxylation of 4-nitrophenol by cytochrome c with hydrogen peroxide

The reaction of hydrogen peroxide with cytochrome c makes them coupled to lead to the hydroxylation of 4-nitrophenol. In situ electrochemical probe was used to detect the hydroxylation of 4-nitrophenol, which can avoid the tedious extraction procedure, the loss of the active species and the interference of some colored substances in the detection of 4-nitrocatechol by spectroscopic method. The hydroxyl radical scavengers mannitol and sodium benzoate did not eliminate hydroxylation, but the inhibitory effect of uric acid on the hydroxylation lead to the formation of the ferryl species of the protein during the reaction. These studies suggest that the electrochemical probe might efficiently detect the trace 4-nitrocatechol from the onset of the hydroxylation reaction and thus provides a more sensitive tool.

Structures and vibrational spectra of C-2 and LaC2+ clusters

C-2 and LaC2+ were studied using Hartree-Fock(HF), B3LYP (Becke 3-paremeter-Lee-Yang-Parr) density functional method, second-order Moller-Plesset perturbation (MP2) and coupled cluster singles and doubles with non-iterative triples(CCSD(T)) methods. The basis set employed was LANL1DZ. Geometries, vibrational frequencies and other quantities were reported. The results showed that for C-2, all the methods performed well for low spin state (singlet), while only HF and B3LYP remained so for high spin state (triplet). For LaC2+, four isomers were presented and fully optimized. The results suggested that linear isomers with C-infinity v and D-infinity h symmetries were predicted to be saddle points on the energy surface for all the methods, while for isomers with C-2 upsilon and C-s symmetries, they were local minima except C-2 upsilon at B3LYP level, and were isoenergetic at HF, MP2 and CCSD(T) levels, near isoenergetic at B3LYP level. From the differences between HOMO and LUMO, it is also known that the isomers with C-2 upsilon and C-s symmetries offer the largest values and therefore correspond to the most stable structure. For La-C bond lengths, B3LYP gives the shortest, the order is B3LYP

Synthesis and crystal structure of chiral bis(cyclopentadienyl) samarium Schiff base complexes bearing intramolecular C-C bond formation and hydrogen transfer

SmCl3, reacted with CpNa (Cp = Cyclopentadienyl) in the ratio of 1:3 in THF, which then was reacted with (S)-(+)-N-1-(phenylethyl) salicylideneamine/toluene to yield the title complex, [GRAPHICS] The X-ray crystal structure determination of the title complex reveals that 1 is a dimer with intramolecular C-C bond formation and hydrogen transfer, which leads to the configuration turnover of the carbon atom at the benzyl position of the ligand, while those of the newly formed asymmetric centers may have either Ii or S type configurations. (C) 1998 Elsevier Science Ltd. All rights reserved.

The electrochemistry of cytochrome c at a viologen-thiol self-assembled monolayer

At the self-assembled monolayer (SAM) of a thiol-functionalized viologen modified gold electrode, cytochrome c (cyt c) exhibits a quasi-reversible electrochemical reaction. The heterogeneous electron transfer rate constant of cyt c in 0.1 mol/L phosphate buffer solution(pH 6.96) is 0.164 cm.s(-1) at 500 mV/s. The adsorbed cyt c on the viologen SAM forms a closely packed monolayer, whose average electron transfer rate is 4.85 s(-1) in the scan range of 50 to 500 mV/s. These results suggest that the SAM of viologen-thiol is a relatively stable, ordered and well-behaved monolayer from an electrochemical standpoint and it promotes the electron transfer process of biomolecules on electrode surface well.

SPES-C与PI共混材料膜的气体除湿性能

以浓硫酸为磺化试剂对聚芳醚砜（ＰＥＳ－Ｃ）进行了磺化改性，得到一系列磺化度不同的产物。采用磺化聚芳醚砜（ＳＰＥＳ－Ｃ）与可溶性聚酰亚胺（ＰＩ）的共混材料制备中空纤维用于空气除湿，研究了磺化度及不同的操作条件对膜除湿性能的影响。结果表明，磺化度适当的ＳＰＥＳ－Ｃ与ＰＩ共混体系不但具有良好的成膜性能，而且膜对水蒸汽具有很高的脱除能力，在操作压力较低（０．２５ＭＰａ）的情况下除湿率可达９５％以上。同时，提高回扫比和操作压力在一定范围内也可以改善这类膜的除湿性能。

La_(1-x)Pr_xP_5O_(14)晶体的发光

Pr~(3+)离子的能级结构丰富,在紫外可见区有很好的荧光发射。因此,以Pr~(3+)为激活离子的发光材料研究工作引起了人们的关注。轻稀土五磷酸盐晶体结构为单斜晶系,空间群为P_(1/2)/C,稀土离子处在隔离的多面体中,离子间的作用减弱,即使在化学计量比的PrP_5O_(14)仍得到激光输出。本文采用水热法生长出La_(1-x)Pr_xP_5O_(14)

Syntheses of indenyl lanthanide derivatives and the molecular structures of [(C9H7)(2)PrCl(THF)](2) and [(C9H7)(3)La(THF)]

The reaction of anhydrous PrCl3 with Na(C9H7) in 1.2 mole ratio in THF gives [(C9H7)(2)PrCl(THF)](2)1. 1 crystallized in monoclinic system, space group P2(1)/c with a = 7.808(2), b = 17.796(6), c = 14.070(4) Angstrom, beta = 93.97(2)degrees, V= 1950.3(9) Angstrom(3), Dcalcd = 1.63 g/cm(3) and Z = 2. Each Pr ion is surrounded by two indenyl, two Cl and one THF in a roughly trigonal bipyramid arrangement with average Pr-C(ring) and Pr-Cl distances of 2.81 and 2.84 Angstrom. The reaction of LaCl3 with Na(C9H7) in 1:3 mole ratio gives (C9H7)(3)LaTHF 2, which crystallizes in the monoclinic space group P2(1)/a with unit cell constants a = 21.871(8), b = 10.585(3), c = 23.652(7) Angstrom,beta = 114.62(2)degrees, V = 4977.9 Angstrom(3) and Z = 8. (C) 1997 Elsevier Science S.A.

SYNTHESIS, SOLUTION DYNAMICS AND X-RAY CRYSTAL-STRUCTURES OF NEODYMIUM-YLIDE COMPLEXES, [(C(5)H(4)R)(3)NDCH2P(ME)PH(2)] (R=H, BU(T))

The interaction of [(C(5)H(4)R)(2)NdCl.2LiCl] (R = H, Bu(t)) with one equivalent of Li[(CH2)(CH2)PPh(2)] in refluxing tetrahydrofuran gave the purplish-blue complex [(C(5)H(4)R)(3)NdCH2P(Me)Ph(2)] in 50% yield. The compounds have been fully characterized by analytical, spectroscopic and X-ray diffraction methods. Variable temperature P-31{H-1} NMR spectroscopy indicated the existence of the following equilibrium: [(C(5)H(4)R)(3)NdCH2P(Me)Ph(2)] + THF reversible arrow (C(5)H(4)R)(3)Nd(THF) + CH2=P(Me)Ph(2). At room temperature, the exchange between the coordinated and free ylide ligand is slow on the NMR time scale.

STRUCTURE OF [LA(NO3)(3)(OH2)(2)(OHME)(BIPY)].15-CROWN-5

[La(NO3)(3)(OH2)(2)(OHMe)(bipy).15-crown-5 is monoclinic, P2(1)/n, with a = 11.239(6), b = 19.302(7), c = 14.458(8) Angstrom, beta = 92.47(5)degrees, and D-calc = 1.63 g cm(-3) for Z = 4. In the complex, two nitrogen atoms (from bipy) and nine oxygen atom

THE CLEAVAGE REACTION OF THE MO-MO TRIPLE BOND - THE CRYSTAL-STRUCTURES OF MOLYBDENUM COMPLEXES [CPMO(CO)(2)(C(5)H(4)NS)], [CPMO(CO)(2)(C(9)H(6)NS)]O=PPH(3) AND [CPMO(CO)(2)(S(2)CNME(2)]

The reactions of [Cp2Mo2(CO)4] (1) with 2,2'-dipyridyl disulphide (C5H4NS-)2, 8,8'-diquinolyl disulphide (C9H6NS-)2 and tetramethyl thiuram disulphide (Me2NC(S)S-)2 in toluene solution resulted in the cleavage of the Mo-Mo triple bond to yield molybdenum complexes [CpMo(CO)2(C5H4NS)] (2), [CpMo(CO)2(C9H6NS)] (3) and [CpMo(CO)2(S2CNMe2)] (4), respectively. The molecular structures of 2, 3 . O=PPh3 and 4 were determined by X-ray diffraction studies. Crystals of 2 are monoclinic, space group P2(1)/n, with Z = 4, in a unit cell of dimensions a = 6.448(1), b = 12.616(2), c = 14.772(2) angstrom, beta = 92.85(1)-degrees. The structure was refined to R = 0.028 and R(w) = 0.039 for 1357 observed reflections. Crystals of 3 . O=PPh3 are triclinic, space group P1BAR, with Z = 2, in a unit cell of dimensions a = 11.351(3), b = 13.409(3), c = 9.895(2) angstrom, alpha = 94.59(2), beta = 90.35(2), gamma = 78.07(2)-degrees. The structure was refined to R = 0.033 and R(w) = 0.037 for 3260 observed reflections. Crystals of 4 are monoclinic, space group P2(1)/a and Z = 4 with a = 12.468(5), b = 7.637(2), c = 13.135(4) angstrom, beta = 96.62(3). The structure was refined to R = 0.032 and R(w) = 0.042 for 1698 observed reflections. Each of complexes 2-4 contains a cyclopentadienyl ligand, a cis pair of carbonyls and a chelate ligand (S,N donor or S,S donor). All the compounds have distorted square-pyramid structures.

细胞色素C在单糖修饰金电极上的直接电化学

Hill等发现在4,4′-联吡啶存在时,细胞色素C在金电极上能进行准可逆的电化学反应。在研究细胞色素C的直接电化学过程中,人们又发现一些生物小分子如氨基酸、嘌呤等对细胞色素C的电化学反应有促进作用,但迄今未见有关糖类分子对细胞色素C电化学反应促进作用研究的报道。本文研究了5种单糖对细胞色素C电化学反应的促进作用。

Ce_xGd_(1-x)P_5O_(14)晶体的生长及其发光特性的光谱研究

本文采用蒸发溶液法生长出一系列 Ce_xGd_(1-x)P_5O_(14)晶体,测定了它们的结构均属于单斜晶系、空间群 P2_1/c,用稳态和时间分辨荧光光谱法研究了该晶体中不同 Gd 含量时的发光性能,观察到随着(1-x)值增加,包含有 Gd~(3+)发射在内的314nm 峰增强和 Ce~(3+)的荧光寿命的有规律递减,说明了存在着 Ce~(3+)至 Gd~(3+)的能量传递。