对金属稀土金属有机配合物的合成、结构及催化性质研究

合成出三类18种双金属稀土金属有机配合物：第一类：Ln-Li双金属π－烯丙基稀土配合物－LiLn(π-C_3H_5)_4 nD(Ln=La、Tb, n=3; Ln=Y、Dy, n=2.5; Ln=Ce、Pr、Nd、Sm、Gd、Er, n=2; D=二氧六环）。第二类：Ln-Mg双金属π－烯丙基稀土配合物-(π-C_3H_5)_2CnCl_5Mg_2(tmed)_2 (Ln=Ce、Nd)和(π-C_4H_7)_2LnCl_5Mg_2(tmed)_2 (Ln=La、Ce、Nd; C_4H_7=i-C_4H_7)。第三类：Ln-Al双金属配合物－[(CF_3CO_2)_3LnHAlR_2·2THF]_2 (Ln=Y、Nd, R=i-Bu; Ln=Eu, R=Et)。用四园X－ray衍射仪在低温下测定了LiCe(π-C_3H_5)_4·4D、[(CF_3CO_2)_3YHAl(i-Bu)_2 2THF]_2、[(CF_3CO_2)_3NdHAl(i-Bu)_2 2THF]_2和[(CF_3CO_2)_3EuHAlEt_2·2THF]_2的晶体结构。对[(CF_3CO_2)_3YHAl(i-Bu)_2·2THF]_2和LiLn(π-C_3H_5)_4 nD类配合物进行了较详细的NMR研究。二维C－H相关NMR谱表明在[(CF_3CO_2)_3YHAl(i-Bu)_2·2THF]_2配合物中6个CF_3CO_2~-有2个羰基的C与H成键，该结果解释了Ln-Al双金属配合物中相应羰基的非平面结构现象。研究表明LiLn(π-CC_3H_5)_4·nD可催化异戊二烯和苯乙烯均聚合；不同配合物中均以Y配合物的活性为最高。(π-C_3H_5)_2CeCl_5Mg_2(tmed)_2对异戊二烯、丁二烯、苯乙烯以及甲基丙烯酸甲酯（MMA）的聚合有较低的催化活性；(π-C_4H_7)_2LnCl_5Mg_2(tmed)_2也对苯乙烯和异戊二烯的聚合有一定的催化活性。分别以LiCe(π-C_3H_5)_4·4D和(π-C_3H_5)_2CeCl_5Mg_2(tmed)_2作为稀土配位催化剂的模型配合物，研究了其催化所得聚异戊二烯的端基结构。表明聚合物均具有烯丙基端基(-CH_2-CH=CH_2)。证明单体在Ce~(3+)和π－烯丙基之间发生了插入反应，聚合按π－烯丙基机理进行。该结果首次为稀土配位催化共轭双烯烃聚合的活性链端π－烯丙基机理提供了直接的实验证据。(π-C_3H_5)_2CeCl_5Mg_2(tmed)_2-Al(i-Bu)_3(Al/Ce(摩尔比)=4))体系对异戊二烯的聚合具有较高的催化活性，所得聚合物仍具有－CH_3-CH=CH_2端基，而没有i-Bu端基。该结果又一次为上述π-烯丙基机理提供了直接的实验证据。发现Ln(CF_3CO_2)_3-AlEt_3体系可催化THF开环聚合。首次实现稀土催化THF开环聚合。研究了Y(CF_3CO_2)_3-HAl(i-Bu)_2-ECH（环氧氯丙烷）体系催化THF开环聚合法性及聚合机理。讨论了各种聚合条件对该体系催化活性的影响。研究了[(CF_3Co_2)YHAl(i-Bu)_2·2THF]_2在ECH存在下催化THF聚合活性并认为该双金属配合物为Y(CF_3CO_2)_3-HAl(i-Bu)_2-ECH体系的活性体。[(CF_3CO_2)_3YHA(i-Bu)_2·2THF]_2和[(CF_3CO_2)_3EuHAlEt_2·2THF]_2均可催化ECH和MMA聚合，所得PMMA的间同(rr)含量可达76.5％。

Chemical Constituents from the Leaves and Stems of Schisandra lancifolia

A new nortriterpenoid, 20-hydroxymicrandilactone D (1) and a novel lignan glycoside, lancilignanside A (2) were isolated from leaves and stems of Schisandra lancifolia, together with three known nortriterpenoids (3—5) and nine known phenolics (6—14). The structures of new compounds 1 and 2 were determined by detailed analysis of their 1D and 2D NMR spectra, and chemical evidences. In addition, compounds 1—2, 6—7, and 9—11 showed anti-human immunodeficiency virus (HIV)-1 activities with 50% effective concentration (EC50) in the range of 3.0—99.0m g/ml. Compound 12 was not bioactive in this assay with EC50 more than 200m g/ml.

Diamond growth by carbon ion implantation of diamond

Medium energy (5-25 keV) C-13(+) ion implantation into diamond (100) to a fluence ranging from 10(16) cm(-2) to 10(18) cm(-2) was performed for the study of diamond growth via the approach of ion beam implantation. The samples were characterized with Rutherford backscattering/channelling spectroscopy, Raman spectroscopy, X-ray photoemission spectroscopy and Auger electron spectroscopy. Extended defects are formed in the cascade collision volume during bombardment at high temperatures. Carbon incorporation indeed induces a volume growth but the diamond (100) samples receiving a fluence of 4 x 10(17) to 2 x 10(18) at. cm(-2) (with a dose rate of 5 x 10(15) at. cm(-2) s(-1) at 5 to 25 keV and 800 degrees C) showed no He-ion channelling. Common to these samples is that the top surface layer of a few nanometers has a substantial amount of graphite which can be removed by chemical etching. The rest of the grown layer is polycrystalline diamond with a very high density of extended defects.

黑土微生物活力与组成对养分添加的响应

东北黑土是我国重要的商品粮生产基地，在保证我国的粮食安全中起着重要作用。鉴于东北黑土所具有的重要战略地位及其面临的严峻形势，如何通过化肥合理配施培肥黑土已经成为一个亟待解决的关键问题。 本文以东北黑土为供试土壤，设置CK、C、N、P、NP、CN、CP、CNP，8个养分组合，进行室内恒温模拟培养。通过对黑土呼吸强度的监测，研究黑土微生物活力对不同养分响应的规律；同时采用磷脂脂肪酸（Phospholipid Fatty Acids, PLFAs）和中性脂肪酸（Neutral Lipid Fatty Acids, NLFAs）为标识物，研究黑土微生物群落结构以及生理生态特性在不同养分条件下的动态变化，揭示黑土微生物活力与群落组成对不同养分响应的规律。 研究结果表明：黑土微生物活力首先受到可利用C源的限制，单加葡萄糖能够使土壤呼吸释放的CO2-C累积量达到对照的10倍以上，使黑土微生物活力显著提高；而在碳限制的状况被缓解后，氮便成为黑土微生物生长的主要限制因素，可利用碳底物充足的条件下，N的加入能够显著提高土壤呼吸强度，使释放出的CO2-C累积量达到对照处理的13倍以上，CN交互作用非常显著；在碳氮养分都充足的条件下，P的施入能更好地刺激微生物生长，提高黑土微生物活力，CNP处理，黑土微生物活力在培养的第3 d即达到峰值。CN和CNP组合能够迅速刺激真菌、细菌生长，使PLFA和NLFA含量、真菌/细菌比值均增加；并且CNP组合优于CN组合。单独加入C和CP组合，不能在短时间内使真菌、细菌的PLFA和NLFA含量显著增加，真菌/细菌比值也处于较低的水平。G+/G-比值在CN条件下，达到最大之后逐渐趋于平稳；而在单加C、CP和CNP条件下，G+/G-比值均在培养时间内达到两次峰值，显示出不同的养分条件下，微生物群落结构发生着内在的动态变化。

5-氟尿嘧啶-β-环糊精结肠靶向前体药物的研究

5-氟尿嘧啶(5-Fluorouracil， 5-FU)是一种抗代谢药物，广泛用于临床治疗结直肠癌、胃癌、乳腺癌等多种癌症，但其首过代谢显著、亲脂性较低，选择性差、毒副作用大。为克服这些缺点人们对5-FU进行了大量的修饰工作，包括小分子修饰以及与各种载体形成微球、微囊、纳米粒、共价前药等。 环糊精(Cyclodextrin，简称CD)，可被结肠中的糖苷酶特异性地降解成小分子糖，而胃和小肠中由于缺乏相应的酶而使环糊精不被降解，这一特性在结肠药物的靶向输送及释放中有重要应用价值。环糊精中含有丰富的羟基，易进行化学修饰，将药物与环糊精通过共价键结合制成前药，使其在胃和小肠中不降解，而在盲结肠中被特异性的酶降解释出药物，达到结肠靶向释药的目的。研究表明，环糊精作为一种前药载体为结肠靶向释药和缓释、控释系统提供了一种有效的手段。 本工作选择5-氟尿嘧啶为模型药物、β-环糊精作为载体，通过中间体5-FU羧酸衍生物的制备及其与β-环糊精的偶联，合成了系列5-FU-β-CD前体药物，并利用紫外、红外、质谱、核磁、元素分析、热分析等手段对其进行结构表征。同时，还研究了前体药物的体外释药性质。具体内容包括： 1. 含有羧基的5-FU衍生物中间体的合成：(5-氟尿嘧啶-1-基)-乙酸(FUAC)、3-(5-氟尿嘧啶-1-基)-丙酸(FUPC)、5-(5-氟尿嘧啶-1-基)-戊酸(FUVC)的合成。 2. 中间体5-FU的羧酸衍生物与β-CD的偶联：分别通过以6-OTs-β-CD为中间体的取代法和活化酯法，合成了第一面取代和第二面取代的5-FU-β-CD大分子前体药物。在二面取代的前体药物制备中，通过改变原料的比例，合成了系列不同取代度(DS)的2-[(5-氟尿嘧啶-1-基)-乙酰基] -β-环糊精结合物。 3. 对上述前体药物进行体外释放研究：分别考察了前体药物在不同pH缓冲溶液中的水解行为及其在小鼠胃肠道人工体液中的酶解行为，并通过UV-Vis及HPLC对前体药物释放情况进行检测分析。 5-Fluorouracil(5-Fu), commonly known as a broad-spectrum antineoplastic drug, has been widely used in the treatment of various kinds of cancer including colon cancer for 40 years. However, this antitumor agent exhibits serious adverse effects, such as their marrow toxicity, gastrointestinal reaction and low selectivity in their clinical use. In order to improve its antitumor activity and reduce its toxicity, the compound was modified in various ways, including the formation of conjugated prodrugs with kinds of carrier, microsphere and nanoparticles etc. Cyclodextrins(CDs) are known to be barely capable of being hydrolyzed and only slightly absorbed in passing through the stomach and small intestine; however they are fermented into small saccharides by colonic microflora and thus absorbed as small saccharides in the large intestine. This biodegradation property of CDs may be useful as a colon-targeting carrier, and thus CD prodrugs may serve as a source of site-specific delivery of drugs to colon. It was demonstrated that prodrugs of CDs can provide a versatile means for construction of not only colon targeted delivery systems, but also delayed release systems. 5-Fluorouracil was taken as a model drug and β-CD as the carrier in this study. Series prodrugs of 5-FU was prepared through the preparation of reactive 5-FU derivatives containing carboxyl group and coupling to hydroxyl groups of CD. The structures of the conjugates were charactered by using IR, UV–vis, ESI-MS, 1H, 13C-NMR spectra, elemental analyses, and thermal analysis. In vitro hydrolysis behavior in aqueous solution and in rat gastrointestinal tract contents of the conjugates were also investigated. The main content of this dissertation includes following aspects: 1. The preparation of 5-FU derivatives containing carboxyl group: 5-Fluorouracil- acetic acid(FUAC)、3-(5-FU-1)-propionic acid (FUPC)、and 5-(5-FU-1)-valeric acid(FUVC). 2. The coupling of 5-FU derivatives to β-CD: 5-FU was selectively conjugated onto the primary or secondary hydroxyl groups of β-CD through an ester linkage, by the substitution of 6-OTs-β-CD and the activated ester method respectively. For the secondary face conjugation, the degree of substitution(DS) can be controlled by changing the mole ratio of the starting materials(FUAC and β-CD). 3. In vitro release behavior of the conjugates in aqueous solution and in rat gastro- intestinal tract contents of the conjugates were investigated, and the reaction was monitored and analyzed by using UV-Vis and HPLC methods.

Measurement of total reaction cross section for neutron-rich nucleus Li-11 on Si-28 target at medium energy

The neutron-rich nucleus Li-11 is separated by the radioactive ion beam line RIBLL at HIRFL from the breakup of 50MeV/u C-13 on Be target. The total reaction cross sections for Li-11 at energies range from 25 to 45MeV/u on Si target have been measured by using the transmission method. The experimental data at high and low energies can be fitted well by Glauber model using two Gauss density distribution. The matter radius of Li-11 was also deduced.

Measurement of neutron-removal cross section of neutron-rich nucleus He-8 by using the transmission method

The neutron-rich nucleus He-8 is selected by RIBLL from the breakup of 50MeV/u C-13 on be target at HIRFL. The 2n-removal and 4n-removal cross section of He-8 was measured by using the transmission method. The point that He-4 is He-8 core can be reduced from the experiment data via the Ogawa's theory.

同中子素核9C、8B、7Be和6Li在中能区与28Si反应总截面的测量

放射性束流(RIB)装置拓广了实验核物理在同位旋(T_z)自由度上从稳定核直到滴线核的广袤空间。通常，位于β-稳定线及其附近的核，N／Z在1－1.5范围变化，其分离能E_s无论对于质子还是中子，总是在6-8 MeV之间；对于远离稳定线的非稳定核，N／Z可在0.5-4范围变化，如~9C的N／Z = 0.5，~(10)He的N／Z = 4，而且分离能E_s是在0-40 MeV之间变化的，开展对这些远离β-稳定线非稳定核性质、结构的研究是目前核物理的前沿之一。核反应总截面σ_R是表征原子核性质特征的一个基本物理量，从实验测得的核反应总截面中可以得到有关核结构和核内核子分布的信息。在由放射性束流所产生奇异核的结构与各种反应机制研究中，反应总截面的测量更是有其特殊的重要性，具有奇异核结构如晕核的一个典型的物理特征就是其反应总截面要比稳定核大得多，Tanihata等人最早就是通过对放射性束流的相互作用截面的测量发现了具有奇异结构的核，即中子晕核。由于反应总截面的测量对探测器的要求不高，而且数据分析过程相对较为简单，因而反应总截面的测量已经成为放射性束核物理的研究的一个非常重要实验手段。中子晕核以及中子皮核的发现促使人们去寻找质子晕核和质子皮核，由于最后一个质子的结合能非常小只有136，keV，并且有较大的电四极矩，因而使得~8B成为质子晕的最大热门候选核，有关~8B是否具有质子晕核结构的问题，许多实验科学家得出了相互矛盾的回答；而目前有关另外一个质子晕候选核~9C的实验数据非常少，目前还没有人从实验上对~9C是否为质子晕核这一问题进行肯定或否定的回答。因此非常有必要测量~9C和~8B的反应总截面。对反应总截面进行研究的一个非常有用理论就是Glauber模型，该模型考虑了库伦效应的多次散射理论。它是一种基于自由核子-核子(N-N)碰撞的与核物质密度相关的理论，因而能够从实验测量到的反应总截面中提取核物质分布的信息。该理论对中低能区的反应总截面描述却有一个缺憾：理论值比实验值都要小。本论文主要描述了利用透射法测量了中能区同中子素核~9C、~8B、~7Be及~6Li与~(28)Si的反应总截面，并介绍了重离子碰撞以及描述重离子性质的几种常用理论。在论文里对实验测量得到的结果进行了理论分析，这些理论包括半经验的Shen公式、Glauber模型、BUU模型以及SHF理论。如果将~9C和~8B当成具有正常核结构来处理，半经验的Shen公式和Glauber模型(HO密度分布)的理论计算值总是比实验值要小得多；对于Glauber模型的理论计算值和实验值的差异，Ozawa等定义了一个差值因子d，方德清等人对轻核系统的d值进行了详细的分析。一般认为，正常核的d值在20％以内，而对于具有晕或皮奇异结构的核，其d值则超过30％，甚至可达50％，因此可根据一个核的d值是否超过30％而且比相邻核的d值明显大这种半经验的方法来判断一个核是否具有奇异结构；利用d值的分析结果，我们认为：~9C和~8B都具有奇异核结构；对于BUU模型用同样的方法引进差值因子d值，对于~9C和~8B有相同的结论。用SHF理论计算得到B和C同位素的密度分布结果显示，~9C和~8B的密度分布比相邻的同位素扩展都要大得多。为减小Glauber模型计算的反应截面与实验值的差别，本论文还对Glauber模型的输入密度形式进行了修改，在原单一HO分布基础上加一个高斯分布的尾巴，并对丰质子的同中子素核~9C、~8B、~7Be及~6Li与~(28)Si靶以及~(12)C和丰中子的C同位素核~(13-16)C与~(12)C靶的反应截面重新进行了计算，结果显示在中能区的计算值比原来单一密度分布的计算结构有明显改善。

Characterization of stable isotope fractionation during methane production in the sediment of a eutrophic lake,lake dagow,germany

We measured delta C-13 of CO2, CH4, and acetate-methyl in profundal sediment of eutrophic Lake Dagow by incubation experiments in the presence and absence of methanogenic inhibitors chloroform, bromoethane sulfonate (BES), and methyl fluoride, which have different specificities. Methyl fluoride predominantly inhibits acetoclastic methanogenesis and affects hydrogenotrophic methanogenesis relatively little. Optimization of methyl fluoride concentrations resulted in complete inhibition of acetoclastic methanogenesis. Methane was then exclusively produced by hydrogenotrophic methanogenesis and thus allowed determination of the fractionation factors specific for this methanogenic pathway. Acetate, which was then no longer consumed, accumulated and allowed determination of the isotopic signatures of the fermentatively produced acetate. BES and chloroform also inhibited CH4 production and resulted in accumulation of acetate. The fractionation factor for hydrogenotrophic methanogenesis exhibited variability, e. g., it changed with sediment depth. The delta C-13 of the methyl group of the accumulated acetate was similar to the delta C-13 of sedimentary organic carbon, while that of the carboxyl group was by about 12 parts per thousand higher. However, the delta C-13 of the acetate was by about 5 parts per thousand lower in samples with uninhibited compared with inhibited acetoclastic methanogenesis, indicating unusual isotopic fractionation. The isotope data were used for calculation of the relative contribution of hydrogenotrophic vs. acetoclastic methanogenesis to total CH4 production. Contribution of hydrogenotrophic methanogenesis increased with sediment depth from about 35% to 60%, indicating that organic matter was only partially oxidized in deeper sediment layers.

Effects of afforestation on soil carbon turnover in China's subtropical region

Afforestation in China's subtropics plays an important role in sequestering CO2 from the atmosphere and in storage of soil carbon (C). Compared with natural forests, plantation forests have lower soil organic carbon (SOC) content and great potential to store more C. To better evaluate the effects of afforestation on soil C turnover, we investigated SOC and its stable C isotope (delta C-13) composition in three planted forests at Qianyanzhou Ecological Experimental Station in southern China. Litter and soil samples were collected and analyzed for total organic C, delta C-13 and total nitrogen. Similarly to the vertical distribution of SOC in natural forests, SOC concentrations decrease exponentially with depth. The land cover type (grassland) before plantation had a significant influence on the vertical distribution of SOC. The SOC delta C-13 composition of the upper soil layer of two plantation forests has been mainly affected by the grass biomass C-13 composition. Soil profiles with a change in photosynthetic pathway had a more complex C-13 isotope composition distribution. During the 20 years after plantation establishment, the soil organic matter sources influenced both the delta C-13 distribution with depth, and C replacement. The upper soil layer SOC turnover in masson pine (a mean 34% of replacement in the 10 cm after 20 years) was more than twice as fast as that of slash pine (16% of replacement) under subtropical conditions. The results demonstrate that masson pine and slash pine plantations cannot rapidly sequester SOC into long-term storage pools in subtropical China.

萤火虫的荧光素酶基因克隆表达及发光行为的初步研究

本研究围绕萤火虫的荧光素酶克隆表达和发光行为两方面来进行。首先对萤火虫的发光体系和发光行为进行了概述，然后对萤火虫荧光素酶cDNA进行了克隆表达分析，探讨了日行性和夜行性萤火虫荧光素酶的差异。最后通过萤火虫的饲养和发光行为观察研究，对卵发光的意义进行了探讨。本研究克隆了三种云南萤火虫的荧光素酶基因，并成功表达出两种有活性的荧光素酶。其中日行性萤火虫云南窗萤(Pyrocoelia pygidialis)的荧光素酶基因完成了首次克隆，并在大肠杆菌中成功表达出有功能的荧光素酶。测序结果表明：P. pygidialis荧光素酶的cDNA序列有1647个碱基，编码548个氨基酸残基。系统发育分析表明云南窗萤与同属三种发光很亮的萤火虫不形成单系，在一定程度上印证了P. pygidialis以及同属微弱发光的日行性种类与持续发出很亮荧光的夜行性种类构成窗萤属两个分支的观点；并且从发光器官的形态差异初步推断这两个分支之间是独立进化的。荧光素酶的结构模拟分析表明，云南窗萤荧光素酶的N端和C端结构域之间的裂沟处存在着五个多肽环，这是已知荧光素酶推测的活性位点。日行性的云南窗萤和三种夜行性萤火虫的荧光素酶有13个不同氨基酸，位于模拟的分子结构表面。这些氨基酸的差异，有利于进一步分析日行性和夜行性萤火虫荧光素酶结构的不同。对栉角雪萤(Diaphanes pectinealis)的荧光素酶cDNA也完成了克隆表达。结果表明其cDNA序列有1647个碱基，编码548个氨基酸残基，比从基因组中获得基因序列多3个碱基。体外表达产物在底物存在时发出黄绿色光。对雌光萤科Rhagophthalmus sp.的荧光素酶基因进行了克隆和氨基酸序列比对。得出其荧光素酶基因与来自同一科的荧光素酶基因有最高的一致性为90.7％，和鞘翅目另外三个科的物种的一致性在65％以下，显示出雌光萤科独特的分类地位。通过对采自昆明郊区的云南窗萤和一种扁萤属萤火虫的饲养和发光行为的观察，得出萤火虫的卵和蛹阶段持续发微弱的光的结论，且首次发现了卵发光在发育过程中的变化。本文对卵发光行为进行了描述，并在此基础上对萤火虫卵和蛹两阶段发光的原因和意义进行了探讨。

Bis(2,2 '-bipyridine)(5,6-epoxy-5,6-dihydro-[1,10] phenanthroline)ruthenium: Synthesis and electrochemical and electrochemiluminescence characterization

In this work, an electrochemiluminescence (ECL) reagent bis(2,2'-bipyridine)(5,6-epoxy-5,6-dihydro-[1,10]phenanthroline)ruthenium complex (Ru-1) was synthesized, and its electrochemical and ECL properties were characterized. The synthesis of Ru-1 was confirmed by IR spectra, element analysis, and H-1 NMR spectra. For further study, its UV-vis absorption and fluorescence emission spectra were investigated. Ru-1 also exhibited quasi-reversible Ru-II/Ru-III redox waves in acetonitrile solution. The aqueous ECL behaviors of Ru-1 were also studied in the absence and in the presence of tripropylamine.

Effect of silver nanoparticles on luminescent properties of europium complex in di-ureasil hybrid materials

Organic-inorganic hybrids containing luminescent lanthanide complex Eu(tta)(3)Phen (tta = thenoyltrifluoroaceton, phen = 1,10-phenanthroline) and silver nanoparticles have been prepared via mixing rare earth complex and nanoparticles with the precursors of di-ureasil using a sol-gel process. The obtained hybrid materials with transparent and elastomeric features were characterized by transmission electron microscope, solid-state Si-29 magic-angle spinning NMR spectra, diffuse reflectance, UV-visible absorption and photoluminescence spectroscopies. The effect of the silver nanoparticles on the luminescence properties was investigated. The experimental results showed that the luminescence intensity of the Eu(tta)(3)phen complex could be enhanced by less than ca. 9.5 nM of silver nanoparticles with the average diameter of 4 nm, and reached its maximum at the concentration of ca. 3.6 nM. Further increasing the concentration of the silver nanoparticles (> 9.5 nM) made the luminescence quenched. The enchancement and quench mechnism was discussed.

Enolic Schiff-base aluminum complexes and their application in lactide polymerization

A series of NNOO-tetradentate enolic Schiff-base ligands were prepared where ligand L-1 = bis(benzoylacetone)propane-1,2-diimine, L-2 = bis(acetylacetone)-propane-1,2-diimine, L-3 = bis-(acetylacetone)cyclohexane-1,2-diimine. Their further reaction with aluminum tris(ethyl) formed complexes LAlEt (1a, 2a and 3a). The solid structure of complexes la, 2a and 3a confirmed by X-ray single crystal analysis manifested that these complexes were all monomeric and five-coordinated with an aluminum atom in the center. The configurations of these complexes varied from trigonal bipyramidal geometry (tbp) to square pyramidal geometry (sqp) due to their different auxiliary ligand architectures. H-1 NMR spectra indicated that all these complexes retained their configuration in solution states. Their catalytic properties to polymerize racemic-lacticle (rac-LA) in the presence of 2-propanol were also studied. The diimine bridging parts as well as the diketone segment substituents had very close relationship with their performance upon the polymerization process. All these complexes gave moderately isotactic polylactides with controlled molecular weight and very narrow molecular weight distributions.

Synthesis and properties of polyimides derived from cis- and trans-1,2,3,4-cyclohexanetetracarboxylic dianhydrides

Cis-1,2,3,4-cyclohexanetetracarboxylic dianhydride (cis-1,2,3,4-CHDA) was synthesized. It was found that under such conditions as heating or boiling in acetic anhydride, cis-1,2,3,4-CHDA could be converted to its trans-isomer. The process of thermal isomerization was monitored by H-1 NMR spectra and the mechanism of conversion was proposed. Their absolute structures of cis- and trans-1,2,3,4-CHDAs were elucidated by single crystal X-ray diffraction. The polycondensations of cis- and trans-1,2,3,4-CHDAs with aromatic diamines such as 4,4'-oxydianiline (ODA), 4,4'-methylenedianiline (MDA), 4,4'-diamino-3,3'-dimethyldiphenylmethane (DMMDA), 4,4'-bis(4-aminophenoxy)benzene (TPEQ), 2,2-bis[4-(4-aminophenoxy)phenyl] propane (BAPP) were studied. It is easy to obtain higher molecular weight polyimides from trans-1,2,3,4-CHDA using conventional one-step or two-step methods. However, higher molecular weight polyimides derived from cis-1,2,3,4-CHDA could not be prepared by the usual methods (solid content ca. 10%) owing to the trend of forming cyclic oligomers.