激波管壁AlO自由基B~2∑~+-X~2∑~+和C~2∏_r-X~2∑~+带系辐射光谱的研究

爆轰驱动过程中产生的高温高压气流对铝质膜片、激波管壁产生烧蚀和冲刷作用,以致激波管壁、端盖上附有氧化铝等杂质,而高温下AlO自由基在气体分子的高速碰撞下被激发并产生强烈的辐射,从而干扰了高温气体辐射光谱的分析。用爆轰驱动加热技术将空气加热到4 000~7 000 K,利用多通道光学分析仪对AlO自由基辐射光谱进行分析,实验发现在460~530 nm波长范围内有多支辐射非常强烈的AlO自由基B2Σ+-X2Σ+(T00=20 689 cm-1)带系辐射谱带,且每支谱带都由多个带头组成,带头间隔约为2 nm,带头处于高频位置并向低频方向伸延。通过实验与理论计算相结合,重点分析了AlO自由基B2Σ+-X2Σ+带系辐射光谱的结构特征。AlO自由基C2Πr-X2Σ+(T00=33 047 cm-1)带系辐射光谱处于270~335 nm波长范围内,其辐射强度相对于B2Σ+-X2Σ+带系较弱,并且与OH基A2Σ+-X2Π(T00=32 682 cm-1)带系辐射光谱互相干扰而难以分辨,对该波段高温空气的辐射光谱分析产生不利的影响。

维生素C发酵中2-酮-L-古龙酸还原酶的研究

由于２酮Ｌ古龙酸还原酶（简称ＫＧＲ）的存在，理论上造成了Ｖｃ合成前体２酮Ｌ古龙酸（简称２ＫＬＧ）部分被还原成Ｌ艾杜糖酸［１，２］，影响了Ｖｃ二步发酵的产率。而从Ｌ山梨糖到２酮Ｌ古龙酸的转化中，除被ＫＧＲ催化的还原负反应外，均属...

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

Bulk modulus of ternary chalcopyrite A(I)B(III)C(2)(VI) and A(II)B(IV)C(2)(V) semiconductors

Based on the complex crystal chemical bond theory, the formula of Liu and Cohen's, which is only suitable for one type of bond, has been extended to calculate the bulk modulus of ternary chalcopyrite A(I)B(III)C(2)(VI) and A(II)B(IV)C(2)(V) which contains two types of bonds. The calculated results are in fair agreement with the previous theoretical values reported and experimental values. (C) 1998 Elsevier Science Ltd. All rights reserved.

Synthesis of the first mono(cyclopentadienyl)lanthanide Schiff base complex bearing C-2-symmetric tetradentate ligand: crystal structure of [(eta(5)-C5H5)Yb(mu-OC20H20N2O)](2)(mu-THF)(THF)

Reaction of YbCl3 with 3 equimolar CpNa (Cp = cyclopentadienide) in THF, followed by treatment with trans-(+/-)-N,N'-bis(salicylidene)-1,2-cyclohexanediamine led to the isolation of first mono(cyclopentadienyl) lanthanide Schiff base complex, [(eta(5)-C5H5)Yb(mu-OC20H20N2O)](2) (mu-THF)(THF) (1). The molecular structure of 1 shows that it is a dimer in which the two [(eta(5)-C5H5)Yb(mu-OC20H20N2O)] units connecting via a bridging THF oxygen and two bridging oxygen atoms from Schiff base ligands. (C) 1998 Elsevier Science S.A.

Synthesis and X-ray crystal structure of [(eta(5)-C5H5)Sm(mu-OC20H20N2O)](2)(mu-THF)(THF)(2): Mono(cyclopentadienyl)lanthanide complex bearing a C-2-symmetric tetradentate Schiff-base ligand

Cp2SmCl(THF) reacts with 0.5 equivalent disodium salts of trans-(+/-)-N,N'-bis(salicylidene)-1,2-cyclohexanediamine give the title complex [(eta(5)-C5H5)Sm(mu-OC20H20N2O)](2)(mu-THF)(THF)(2) (1). X-ray crystal determination shows that the molecule is a dimer, in which two (eta(5)C(5)H(5))Sm(mu-OC20H20N2O) units are connected via a THF oxygen and two bridging oxygen atoms of Schiff base ligands. The average Sm-C distance is 2.78(7) Angstrom, while those of Sm-O (bridging THF oxygen) and Schiff base oxygens are 2.79(3) and 2.43(4) Angstrom; respectively. (C) 1998 Elsevier Science Ltd. All rights reserved.

栉孔扇贝C型凝集素-2(CfLec-2)基因的克隆和分析

栉孔扇贝是我国北方一种重要的贝类养殖品种。自1997年以来爆发的栉孔扇贝大规模死亡，给地区经济造成了重大损失并且已经严重威胁着扇贝养殖业的健康发展。然而，到目前为止，对扇贝免疫防御分子机理的了解还很少，深入研究扇贝免疫应答的分子机制是认识和了解病害发生和实现病害控制的重要途径。本研究采用了EST大规模测序和3’RACE的方法，从栉孔扇贝cDNA文库中克隆到一个凝集素基因CfLec-2，并对功能进行了研究。 CfLec-2 cDNA全长708bp，5’非翻译区(Untranslated Region, UTR)含有59bp，3’非翻译区含有163bp，具有典型的多聚腺苷酸加尾信号序列AATAAA和多聚腺苷酸尾巴，开放阅读框(Open Reading Frame, ORF )含有486bp，编码162个氨基酸残基，该多肽的理论分子量为16.8 kDa，等电点为4.54。利用SignalP分析，发现其信号肽的剪切位置在VEA-QSL之间。经BLASTP比对分析可知，CfLec-2基因编码的蛋白与人的Brevican，Anguilla japonica的C-type lectin-1和C-type lectin-2， Rattus norvegicus的CD23有较高的相似性，其中与Brevican的一致性有37%。Clustal W多序列比对发现该多肽具有标准长型C型凝集素所必须的6个保守半胱氨酸和相对保守的糖识别位点。用SMART(Small Modular Architecture Research Tool)软件分析发现其具有一个保守的糖识别结构域(Carbohydrate-recognition Domain, CRD)，氨基酸序列上第49、125、141、149位置上的半胱氨酸参与形成糖识别结构域，而位于N末端的第21和32位上的两个半胱胺酸形成额外的一个二硫键，位于115、116和117上的Glu、Pro、Asp则构成了糖识别位点。 将编码CfLec-2成熟肽段的cDNA序列克隆进pET32a(+)载体中，并在大肠杆菌Rosetta-gami(DE3)中重组表达CfLec-2。重组蛋白利用其具有的His tag纯化并复性后发现CfLec-2可以凝集溶血葡萄球菌，且凝集过程不需要钙离子的参与。并且，CfLec-2对大肠杆菌TOP10F’有微弱的抑菌活性，对溶壁微球菌、溶血葡萄球菌和鳗弧菌则没有抑菌活性。这一结果说明，CfLec-2可能不仅参与对入侵微生物的识别过程，而且可能作为效应分子起到了直接杀灭入侵微生物的作用。 本研究发现CfLec-2具有和以前在栉孔扇贝报道的CFLec-1完全不同的功 能，说明栉孔扇贝利用不同的凝集素来识别不同的病原，同时也暗示栉孔扇贝中可能有更多不同功能的凝集素有待发现。研究结果丰富和发展了海水无脊椎动物免疫学的内容，对进一步了解扇贝固有免疫的机制，实现养殖扇贝疾病防治具有重要参考价值。

Influence of iron promoter on catalytic properties of Rh-Mn-Li/SiO2 for CO hydrogenation

The effect of iron promoter on the catalytic properties of Rh-Mn-Li/SiO2 catalyst in the synthesis Of C-2 oxygenates from syngas was investigated by means of the following techniques: CO hydrogenation reaction, temperature-programmed reduction (TPR), temperature-programmed desorption and reaction of adsorbed CO (CO-TPD and TPSR) and pulse adsorption of CO. The results showed that the addition of iron promoter could improve the activity of the catalysts. Unexpectedly, the yield of C-2 oxygenates increased greatly from 331.6 up to 457.5 g/(kg h) when 0.05% Fe was added into Rh-Mn-Li/SiO2 catalyst, while no change in the selectivity to C-2 oxygenates was observed. However, the activity and selectivity Of C-2 oxygenates were greatly decreased if the Fe amount exceeded 1.0%. The existence of a little iron decreased the reducibility of Rh precursor, while the reduction of Fe component itself became easier. CO uptake decreased with increasing the quantity of Fe addition. This phenomenon was further confirmed by CO-TPD results. The CO-TPD and TPSR results showed that only the strongly adsorbed CO could be hydrogenated, while the weakly adsorbed CO was desorbed. We propose that Fe is highly dispersed and in close contact with Rh and Mn; such arrangements were responsible for the high yield Of C-2 oxygenates. (C) 2002 Elsevier Science B.V. All rights reserved.

Different mechanisms for the formation of acetaldehyde and ethanol on the Rh-based catalysts

Different mechanisms for the formation of acetaldehyde and ethanol on the Rh-based catalysts were investigated by the TPR (temperature programmed reaction) method, and the active sites were studied by CO-TPD, TPSR (temperature programmed surface reaction of preadsorbed CO by H-2) and XPS techniques. The TPR results indicated that ethanol and acetaldehyde might be formed through different intermediates, whereas ethanol and methanol might result from the same intermediate. Results of CO-TPD, TPSR, and XPS showed that on the Rh-based catalyst, the structure of the active sites for the formation of C-2-oxygenates is ((RhxRhy+)-Rh-0)-O-Mn+ (M=Mn or Zr, x>>y, 2 less than or equal ton less than or equal to4). The tilt-adsorbed CO species is the main precursor for CO dissociation and the precursor for the formation of ethanol and methanol. Most of the linear and geminal adsorbed CO species desorbed below 500 K. Based on the suggested model of the active sites, detailed mechanisms for the formation of acetaldehyde and ethanol are proposed. Ethanol is formed by direct hydrogenation of the tilt-adsorbed CO molecules, followed by CH2 insertion into the surface CH2-O species and the succeeding hydrogenation step. Acetaldehyde is formed through CO insertion into the surface CH3-Rh species followed by hydrogenation, and the role of the promoters was to stabilize the intermediate of the surface acetyl species. (C) 2000 Academic Press.

The effect of Rh particle size on the catalytic performance of porous silica supported rhodium catalysts for CO hydrogenation

Silica-supported Rh catalysts with different Rh particle dimensions were investigated for CO hydrogenation. The catalysts were characterized by various techniques such as TEM, H-2-TPR and N-2 adsorption to study the catalyst morphology, the size distributions of Rh particles and the silica pores. It was found that the distribution and the size of Rh particles were affected by the silica pores, and the metal grains were enclosed in the pores of the support, and thereby their growth was limited. The catalytic activity and selectivity to C-2-oxygenates for CO hydrogenation were found to be significantly controlled by the Rh particle sizes, and the higher activity and selectivity to C2-oxygenates were obtained over bigger Rh particles, within the range of the reported particle sizes.

2-C-支链-1,6-脱水吡喃葡萄糖的开环反应及吡喃烯糖的合成研究

在糖化学合成中，1,6-脱水吡喃糖不仅是合成具有生物活性低聚糖、糖共体、抗原、抗体以及天然产物等化合物重要原料，而且还是许多具有生物活性的天然产物的结构单元。同时，它还具有[3,2,1]的双环缩醛结构，使其在糖化学合成中具有高的立体选择性和区域选择性，同时减少了C-1 和C-6 位的保护和去保护的优点。此外，环内的缩醛开环后，又可以相应地在C-1 和C-6 位进行官能团转化以及糖苷化反应。 本文报道了一种新的1,6-脱水吡喃糖的合成方法，并设计合成了2-C-支链-1,6-脱水吡喃葡萄糖1-195、1-197、1-198 以及2-C-支链-6-硫代1,6-脱水吡喃葡萄糖1-225。到目前为止，1,6-脱水糖开环并进行糖苷化反应，存在选择性较差、产率低的缺点。我们发现，在乙腈做溶剂的条件下，NiCl5 能高立体选择性高产率地催化化合物1-195、1-197、1-198 开环并与ROH、RSH 发生糖苷化反应。在NiCl5-乙腈条件下，合成了一系列2-C-支链-α-糖苷和2-C-支链-β-硫代糖苷，并对2-C-支链1,6-脱水吡喃葡萄糖的生成机理以及开环机理进行了探讨。 烯糖在糖化学合成中是重要的起始原料，从Fischer 首次合成烯糖至今，一直不断地有新的合成方法出现。但目前文献报道的方法存在所用试剂有毒、价格贵和操作繁琐等缺点。我们对Fischer-Zach 方法进行了改进， 发现Zn-NaH2PO4-H2O 和Zn-PEG600-H2O 体系都能很好地合成烯糖。该方法具有条件温和、绿色环保、操作简单的优点。在Zn-NaH2PO4 溶液或Zn-PEG600 条件下，以溴代糖为原料，高产率地合成一系列的烯糖。 The 1,6-anhydrohexopyranoses are crucial subunits of myriad bioactive nature products, as well as important syntons of carbohydrate chemistry which have been extensively used to prepare the biologically potential oligosaccharides, glycoconjugates, antibiotics, and structurally varied nature products. Their particular [3.2.1] bicyclic skeleton makes them have high regio- and stereo-control in a variety of reactions, and such structure avoids protecting hydroxyl groups at C1 and C6.Additionally, the cleavage of the internal acetal under acidic conditions could be beneficial for further transformations of functional group and glycosylation of the corresponding pyranosyl sugar at the C6 or C1 site. Herein we developed a novel approach to prepare the 1,6-anhydrohexopyranose, and synthesized the 2-C-branched-1,6-anhydrohexopyranose 1-195, 1-197, 1-198 and 2-C-branched-6-thio-1,6-anhydrohexopyranose 1-225. Until now, glycosylation of 1,6-anhydrohexopyranoses has been limited because of the low yields and low stereoselectivity. In this paper, we found that NiCl5-MeCN system could selectively cleave the ring of 1,6-anhydrohexopyranoses with alcohols and thiols at room temperature in high yields. A series of 2-C-branched-α-glycosides and 2-C-branched-β-thioglycosides have been synthesized via NiCl5-catalyzed. Furthermore, we investigated the formation and ring-opening mechanism of 2-C-acetylmethyl-1,6-anhydrohexopyranose. Glycals are significant starting material in carbohydrate chemistry. After the Fischer-Zach method for forming glucal was reported for the first time, the numerous synthetic methods for glycals have been explored. However, there are several drawbacks in the existing methods, such as the usage of very expensive and toxic reagents, intricate operation, and the influence of acid-sensitive and base-sensitive functional group. We improved the Fischer-Zach method and developed a facile, mild and environmentally benign methodology towards the synthesis of the glycals in Zn-NaH2PO4-H2O or Zn-PEG600-H2O system. Our method involves the treatment of glycosyl bromides with Zn in NaH2PO4 aqueous solution or PEG600-H2O at room temperature, affording various glycals in excellent yields.

A new zirconocene complex, [{eta(5)-C5H4-C(CH2)(5)(CH2)(2)CH(CH3)(2)}2ZrCl2]

The title compound, dichlorobis{eta(5)-[1-(3-methylbutyl)-cyclohex-1 -yl]cyclopentadienyl}zirconium(IV), [ZrCl2-(C16H25)(2)], has a pseudo-tetrahedral bent-metallocene structure in which the substituted cyclopentadienyl rings are asymmetrically bonded to the central Zr atom, due primarily to the interaction between the large substituents and the Cl atoms. The molecule has local C-2 symmetry with the substituents positioned in a trans arrangement and directed towards the lateral sectors of the bent-metallocene unit.

2,2′-联吡啶的吸附行为与其对细胞色素c电化学反应的促进作用

2,2′-联吡啶在金电极上需长达10 h 左右才能达到吸附平衡和有足够量的分子来促进细胞色素 c 的电化学反应.需用长时间浸泡膜转移法,减小因促进剂分子吸附强度的变化而造成的差别.

Structure and anti-HIV activity of micrandilactones B and C, new nortriterpenoids possessing a unique skeleton from Schisandra micrantha

Two new highly oxygenated nortriterpenoids with a unique norcycloartane skeleton, micrandilactones B and C (1-2), were isolated from Schisandra micrantha; micrandilactone C ( 2) exhibited an EC50 value of 7.71 mu g/mL (SI > 25.94) against HIV-1 replication with minimal cytotoxicity, and the potent anti-HIV-1 activity and unique structural features of 2 make it a promising lead for therapeutic development of a new generation of anti-HIV drug.