聚-4,7-二硫杂壬基倍半硅氧烷铑配合物的合成与催化硅氢化性能

本文叙述了一种新型有机硅聚合物负载配位催化剂——聚-4,7-二硫杂壬基倍半硅氧烷铑配合物的合成、结构及其对烯烃硅氢化反应的催化性能.标题配合物在用量为烯烃摩尔量的十万分之一时仍具有良好的催化活性,烯烃的转化数达到80,000.     

MOLECULAR WEIGHT DISTRIBUTION OF AB, A, TYPE CONDENSATION POLYMERS OBTAINED BY ADDING AB MONOMERS IN BATCHES

The molecular weight distribution (MWD) and arm length distribution of AB, Ar type condensation polymers obtained by adding AB monomers in batches have been derived by statistical and kinetic methods. Calculations show the MWD of condensation polymers obtained by this process is much narrower than that of one batch reaction and agrees with the Monte Carlo results very well.     

Comparative X-ray photoelectron spectroscopic study on the desulfurization of thiophene by Raney nickel and rapidly quenched skeletal nickel

The desulfurization of thiophene on Raney Ni and rapidly quenched skeletal Ni (RQ Ni) has been studied in ultrahigh vacuum (UHV) by X-ray photoelectron spectroscopy (XPS). The Raney Ni or RQ Ni can be approximated as a hydrogen-preadsorbed polycrystalline Ni-alumina composite. It is found that thiophene molecularly adsorbs on Raney Ni or RQ Ni at 103 K. At 173 K, thiophene on alumina is desorbed, while thiophene in direct contact with the metallic Ni in Raney Ni undergoes C-S bond scission, leading to carbonaceous species most probably in the metallocycle-like configuration and atomic sulfur. On RQ Ni, the temperature for thiophene dissociation is about 100 K higher than that on Raney Ni. The lower reactivity of RQ Ni toward thiophene is tentatively attributed to lattice expansion of Ni crystallites in RQ Ni due to rapid quenching. The existence of alumina and hydrogen may block the further cracking of the metallocycle-like species on Raney Ni and RQ Ni at higher temperatures, which has been the dominant reaction pathway on Ni single crystals. By 473 K, the C 1s peak has disappeared, leaving nickel sulfide on the surface.     

ZrO2对合成二甲醚双功能催化剂表面结构及催化性能的影响

采用共沉淀沉积法制备了Cu基双功能催化剂，并进行了合成气一步法制取二甲醚实验．XRD、XPS以及BET表征结果表明，催化剂中ZrO2以无定形状态存在，且随着其含量的增加，Zr^4 逐渐溶进CuO晶格，两者之间的电子交换使得Cu^2 在活化过程中很难被彻底还原为Cu^0，而是以Cu^0/Cu^ 的形式共存．活性评价结果表明，Cu^ 离子表现出优异的CO转化率和DME选择性．同时，ZrO2的存在能有效调节催化剂表面的Cu／Zn摩尔比以及促进Cu元素在表面的富集，从而改善催化剂性能．     

Co-immobilization of polymeric luminol,iron(II) tris(5-aminophenanthroline) and glucose oxidase at an electrode surface,and its application as a glucose optrode

The anodic polymerization of 3-aminophthalhydrazide (luminol) and iron(II) tris 5-aminophenanthroline (Fe(phen-NH2)3(2+)) has been reported in this paper. A bilayer electrode was developed based on these polymers and the ITO conductive glass (denoted ITO[Fe(phen-NH2)3(2+)]luminol electrode). This electrode emitted light (lambdaem: 430 nm) as it was brought into contact with H2O2. At pH 10, the resulting electrochemiluminescence (ECL) showed a linear relationship with the concentration of H2O2 in the range of 10 microM(-1) mM. This bilayer electrode also showed an application potential for the detection of glucose after being further modified with glucose oxidase (denoted ITO[Fe(phen-NH2)3(2+)]luminol]GOx electrode). Although the resulting ECL decayed more rapidly in concentrated glucose solutions (e.g., I M) because of the consumption of luminol during use, the decay became less severe in diluted glucose solutions (e.g., 10 mM). According to the flow injection analysis, a linear relationship existed between the ECL and the concentration of glucose from 10(-5)-10(-3) M at pH 9. The detection limit could reach a level of 5 x 10(-5) M at this pH.     

稀土在鼠肝中的物种分布

采用 ICP-MS、微量蛋白层析分离技术 ,研究了长时间、低剂量混合稀土及短时间、高剂量硝酸镧分别对大鼠及小鼠作用后 ,稀土在鼠肝中的代谢累积及其物种分布 .结果表明 ,鼠肝中各稀土含量随给药剂量的增加而增大 ,其累积速度大小顺序为 La>Ce>Nd>Pr;经柱层析分离未得到与稀土特异结合的鼠肝蛋白 ;稀土可与多种鼠肝蛋白 (包括多种重要的酶 )结合 ,在一定条件下 ,稀土与其结合蛋白可发生解离     

SYNTHESIS AND CATALYTIC PROPERTY OF POLYSTYRENE SUPPORTED GLUTAMIC ACID SCHIFF BASE COMPLEX OF Mn（ Ⅱ ） IN AEROBIC OXIDATION OF CYCLOHEXENE

The polystyrene supported glutamic acid Schiff base complex of Mn （ Ⅱ ） （PS-Sal-Glue-Mn） was prepared with chloromethylated styrene polymer beads, 2,4-dihydroxybenzaldehyde, L-glutamic acid and manganese （ Ⅱ ） acetate tetrahyrate. The polymeric ligand and the complex were characterized by FT-IR, small area X-ray photoelectron spectroscopy （XPS） and 1CP-AES. In the presence of the manganese complex, cyclohexene （1） was effectively oxidized by molecular oxygen without reductant. The major products of the reaction were 2-cyclohexen-l-ol （2）, 2-cyclohexen-l-one （3） and 2-cyclohexen-1- hydroperoxide （4）, which was different with typical oxidation of cyclohexene. The influence of reaction temperature and additive for oxidation had been studied. The selectivity of 2-cyclohexen-1-hydroperoxide varied with reaction time and different additives. The mechanism of cyclohexene oxidation had also been discussed.     

激光核聚变中的一种X光解谱方法

本文在SAND迭代法的基础上,采取带有周期性光滑化的限幅迭代方法,求解激光核聚变中的X光能谱取得了较好的结果。这个方法适用于根据亚千X射线谱仪、多道k边滤波谱仪和多道滤波-荧光谱仪的测量结果回推靶等离子体的X射线能谱。计算结果表明,该方法完全抑制了数值不稳定性,消除了非物理的“负能谱”现象和解谱结果中的数值结构。特别是该方法对初始试探谱有很强的适应性,解谱计算结果与初始试探谱无关。     

Ligand Exchange Between Penta-Coordinated Phosphoryl Serine and Histidine Compounds

With the assistance of HPLC-ESI-MS/MS, the self-assembly products of serine and histidine penta-coordinated phosphorus compound were separated and identified. The expectative product was seryl-histidine dipeptide, but it was found that there was almost equimolar amount of histidyl-histidine dipeptide as well as seryl-histidine dipeptide. The mechanism was speculated that there was iigand exchange between penta-coordinated phosphoryl serine and histidine in the reaction process. As a result,two types of dipeptide were produced.     

Crystal Structure of Dimethylamine 3,5-Dinitrobenzoic Acid Organic Adduct

1 INTRODUCTION Nonlinear optics (NLO) is at the forefront of cur- rent researches because of its importance in provi- ding the key functions of frequency shifting, optical modulation, optical switching, optical logic and op- tical memory for the emerging …