可生物降解聚酯及其共聚物的合成

生物降解高分子材料是当今高分子材料领域的研究热点。本论文引入了一种新型的催化剂－Ca���化剂用于合成生物降解高分子PCL及其嵌段共聚物PEO－PCL、PEO－PCL－PEO、PCL－PEO，另外对嵌段共聚物PLLA－PEO的合成也做了探索性的研究。实验结果表明：1、Ca���化剂从氨钙配合物出发制备，利用各种不同的配体对其配位（如已内酯、环氧丙烷和乙腈），并在适当温度下加热陈化，催化活性得到明显的改善。2、Ca���化剂可以高效催化已内酯的聚合。详细讨论了Ca���化剂催化已内酯聚合的聚全条件。在室温至100 ℃，钙催化剂均能有效催化已内酯聚合，单体转化率接近100%。随着单体与催化剂的比值M／I、聚合温度和时间的变化聚合物的分子量MW发生相应的变化。MW与M／I的线性关系说明了钙催化剂聚合已内酯的准活性特征。高的聚合温度可以获得主的转化率，但聚合物分子量却相应降低。在一定的聚合时间内MW随着聚合时间的增加而增加，但如果聚合时间过长MW会有所降低，分子量分布变宽，说明聚合后期随着单体的减少降解反应和微量的酯交换反应显著。最高分子量出现在25万到30万左右。另外，对聚合物做了几种力学测试（强度S、模量E和伸长率σ），发现随着PCL分子量的增加，上述几种力学性能发生相应的变化。MW在20万左右时S＝28MPa，E=256MPa，σ=743%。3、 Ca���化剂既可以制备PEO－PCL嵌段共聚物，也可以制备PCL－PEO嵌段共聚物。在两种共聚物的基础上还可以继续制备三嵌段共聚物。此外，Ca���化剂还可以用于制备嵌段共聚物PLLA－PEO。通过NMR，GPC，DSC等测试手段证明所得的共聚物确实为嵌段共聚物。

Influence of heat treatment on spectroscopic properties of Er3+ in multicomponent ZrF4-ZnF2-AlF3-YF3-MF2 (M = Ca, Sr, Ba) based glass

Er3+ doped multicomponent fluoride based glass was prepared. These precursor fluoride glass samples were then heated using different schedules. Crystalline phase particles were successfully precipitated in the multicomponent fluoride glass samples after heat treatment. The influence of heat treatment on the spectroscopic properties of Er3+ in multicomponent fluoride based glass samples were discussed. Small changes of the Judd-Ofelt parameters Omega(i) (i = 2,4,6) were found in multicomponent fluoride glass samples before and after heat treatment compared to oxyfluoride telluride glass. Preparation conditions used to produce transparent multicomponent fluoride glass ceramics doped with rare-earth ions are discussed. (c) 2007 Elsevier B.V. All rights reserved.

I.小麦非叶器官碳酸酐酶活性与定位分析II.镉毒害导致芦苇胚性细胞死亡的激素调控研究

第一部分： 通过生理测定和化学染色分析了冬小麦品种小堰54和京411的叶片和非叶片组织的碳酸酐 酶活性。叶片碳酸酐酶活性(CA)在挑旗时期达到最大值，之后减少到最小，而在饱粒期又呈 增加趋势。从灌浆期到饱粒期，颖片和内稃的CA���性均减少，而外稃和种皮的CA���性均增加。在饱粒期，小堰54的叶片、颖片、外稃和种皮CA���性均高于京411。组织化学染色表明，CA���要分布在旗叶的叶肉细胞叶绿体中，也分布在非叶片组织颖片、外稃和内稃的叶肉和维管束鞘细胞的胞质中。这些结果表明，小麦非叶组织叶肉和维管束鞘细胞的胞质中的CA���能对饱粒期冬小麦的C4光合途径起作用。饱粒期小堰54的C02传递到Rubisco酶速率和抗旱性较京411高。 第二部分： 以继代培养的芦苇胚性细胞为材料，利用台盼兰拒染法检测了悬浮细胞死亡过程，并利用石蜡切片法及苏木精染色法观察了不同浓度镉对芦苇细胞的毒害作用。1000μM的CdCl2迅速导致芦苇悬浮细胞死亡，200μM的CdClz在接种后第5天引起悬浮细胞死亡，100μM的CdCl2在接种后第7天引起悬浮细胞死亡，≤50μM的CdClz在接种后7天不引起悬浮细胞死亡。同时对不同浓度镉处理的芦苇胚性细胞的内源植物激素和可溶性蛋白质进行分析，≤50μM的镉浓度显著地降低胚性细胞内IAA、ZR、GA3和GA4的含量，却提高ABA的含量，抑制可溶性蛋白质的合成：≥100μM的镉浓度显著地提高IAA、ZR、GA3和GA4的含量，却降低ABA的含量，促进可溶性蛋白质的合成。这些结果表明，镉的毒害至少包括镉浓度决定的两种细胞死亡机制，高浓度的镉(1000μM)引起的细胞死亡应当为坏死，而100μM的镉引起植物悬浮细胞发生程序性死亡。在较高浓度(≥100μM)的镉处理下，芦苇细胞内内源IAA、ZR、GA3和GA4的浓度较高，可能调控可溶性蛋白质的合成而促进细胞发生程序化死亡。

Ca 2+对叶绿体膜流动性及光系统II叶绿素蛋白质复合物的影响

通过实验我们证明Ca2+对叶绿体膜的流动性，对PS I和PS II叶绿素蛋白质复合物的相对含量，以及PS I和PS II的多肽均有影响。 Ca2+对叶绿体膜表层的流动性影响不大，但降低了叶绿体膜深层脂质分子的流动性。从另一个角度阐明了Ca2+抑制光能从PS II向PS I传递的机制。 Ca2+可使PS I的21，23，110KD的多肽转移至PS II，LHCP1和LHCP2中的CF1的两个亚基（55，60KD）转至CPa和LHCP3，从而增加了PS II的捕光截面，引起激发能在两个系统之间的分配的改变。 用免疫学方法可以证明CPIa2和LHCP2的Ab为复合抗体，CPIa1的Ab为单抗，我们可以推测向日葵的不同叶绿素蛋白质复合物具有同源性。

Synthesis, photoluminescence, and theoretical studies of novel Cu(I) complex

A novel diimine Cu(I)complex [Cu(ABPQ)(DPEphos)]BF4 [ABPQ and DPEphos are acenaphtho[1,2-b]bipyrido[2,3-h:3,2-f]quinoxaline and bis(2-(diphenylphosphanyl)phenyl) ether, respectively] is synthesized, and its photophysical properties are experimentally and theoretically characterized. The emission bands centered at ca. 400/470 and 550 nm of [Cu(ABPQ)(DPEphos)]BF4 are attributed to the ligand-centered pi -> pi* transition and the metal-to-ligand charge transfer d pi(Cu) -> pi*(N-N) transition, respectively. The luminescence quantum yield of [Cu(ABPQ)(DPEphos)]BF4 in CHCl3 is found to be about five times higher than that of [Cu(Phen)(DPEphos)]BF4.

Synthesis, photophysical properties, and theoretical studies on pyrrole-containing bromo Re(I) complex

Two bromo rhenium(I) carbonyl complexes with the formula of [Re(CO)(3)(L)Br], where L = 1,10-phenanthroline (Phen-Re) and 5-(1H-pyrrol-1-yl)-1,10-phenanthroline (Pyph-Re), were successfully synthesized with the aim to analyze the effect of the pyrrole (Py) moiety on the photophysical properties of Pyph-Re. It was found that the triplet metal-to-ligand charge-transfer d pi (Re) --> pi*(N-N) emission of Phen-Re and Pyph-Re centered at ca. 527 nm with the luminescence quantum yield (LQY) of 0.015 and ca. 578 nm with the LQY of 0.011, respectively. At the same time, the geometrical structures of the ground state and the absorption spectral properties of Phen-Re and Pyph-Re were also calculated with the 6-31G* basis set employed on C, H, N, O, and Br atoms, and LANL2DZ adopted on Re atom.

Highly efficient electroluminescence from green-light-emitting electrochemical cells based on Cu-I complexes

The complexes [Cu(dnpb)(DPEphos)](+)(X-) (dnpb and DPEphos are 2,9-di-n-butyl-1,10-phenanthroline and bis[2-(diphenyl-phosphino)phenyl]ether, respectively, and X- is BF4-, ClO4-, or PF6-) can form high quality films with photoluminescence quantum yields of up to 71 +/- 7%. Their electroluminescent properties are studied using the device-structure indium tin oxide (ITO)/complex/metal cathiode. The devices emit green light efficiently, with an emission maximum of 523 nm, and work in the mode of light-emitting electrochemical cells. The response time of the devices greatly depends on the driving voltage, the counterions, and the thickness of the complex film. After pre-biasing at 25 V for 40 s, the devices turn on instantly, with a turn-on voltage of ca. 2.9 V. A current efficiency of 56 cd A(-1) and an external quantum efficiency of 16% are realised with Al as the cathode. Using a low-work-function metal as the cathode can significantly enhance the brightness of the device almost without affecting the turn-on voltage and current efficiency. With a Ca cathode, a brightness of 150 cd m(-2) at 6 V and 4100 cd m(-2) at 25 V is demonstrated. The electroluminescent performance of these types of complexes is among the best so far for transition metal complexes with counterions.

Selective separation of yttrium by CA-100 in the presence of a complexing agent

The selective separation of Y from yttrium solution containing small heavy rare earth (HRE) impurities (Ho, Er, Tm, Yb, Lu) by liquid-liquid extraction using CA-100 in the presence of a water-soluble complexing agent of ethylenediaminetetraacetic acid (EDTA) was experimentally studied at 298K. Experiments were carried Out in two feeds, Feed-I: [RE](f) = 4.94 x 10(-3) M, Y = 98.5%, HRE (Ho, Er, Tm, Yb, Lu) = 1.5%; Feed-II: [RE](f) = 4.94 x 10(-3) M, Y = 99.9%, HRE (Ho, Er, Tm, Yb, Lu) = 0.1%, as a function of equilibrium pH (pH(eq)), the concentration ratio of [EDTA]:[HRE impurities]. It was shown that the extraction of HRE in the presence of EDTA was suppressed when compared to that of Y because of the masking effect, while the selective extraction of Y was enhanced and the separation factors increased to maximum at appropriate condition for Feed-I: Y/Ho = 1.53, Y/Er = 3.09, Y/Tm = 5.61, Y/Yb = 12.04, Y/Lu = 27.51 at pH 4.37 and [EDTA]:[HRE impurities] = 4: 1, for Feed-II: Y/Ho = 1.32, Y/Er = 1.91, Y/Tm = 2.00, Y/Yb = 3.05, Y/Lu = 3.33 at pH 4.42 and [EDTA]: [HRE impurities] = 8:1. The separation and purification of Y by this method was discussed.

A STUDY ON THE LUMINESCENCE PROPERTIES OF EU3+ AND DY3+ IN M(2)RE(8)(SIO4)(6)O-2 (M=MG, CA RE=Y, GD, LA)

In this paper, the luminescence properties of Eu3+ and Dy3+ in the oxyapatites M(2)RE(8)(SiO4)(6)O-2 (M=Mg, Ca; RE=Y, Gd, La) were studied. The spectral characters of Eu3+ were discussed in relation to the crystal structure. The dependence of the red-to-orange intensity ratio and the position of the charge transfer band of Eu3+ and the yellow-to-blue intensity ratio of Dy3+ together with their fluorescence intensities (I-R for Eu3+ and I-Y for Dy3+) On the M(2+) and the substitution of BO45- and PO43- for SiO44- was discussed. Finally, the concentration quenching of Dy3+ luminescence was reported.

STUDIES ON THE COORDINATION OF TB(III) AND CA(III) WITH AMINO-ACID UNDER THE PHYSIOLOGICAL CONDITION

Tb(Ca)-glycine, Tb(Ca)-alanine, Tb(Ca)-glycine-alanine systems were studied by potentiometry (37%, I = 0.15 mol/L NaCl). The stability constants of complexes and distribution of species in ternary system were obtained. The results show Ca<Tb for the stability of binary complexes, Ca>Tb for the ternary complexes. The species convert each other with changing pH values.

INVOLVEMENT OF CA(2+) SIGNALING PATHWAY DURING OOCYTE MATURATION OF THE NORTHERN QUAHOG MERCENARIA MERCENARIA

In many molluses, it has been found that Ca2+ signaling pathway is involved in the resumption of meiotic maturation in oocytes. To better understand the possible role of Ca2+ signaling pathway in regulating meiotic maturation in oocytes of the northern quahog Mercenaria mercenaria, free extracellular Ca2+, A23187 (calcium ionophore), verapamil (calcium channel blocker), and trifluoperazin (calmodulin antagonist) were used to incubate oocytes or serotonin-induced oocytes by pharmacological methods. Results show that extracellular Ca2+ (50 similar to 200 mM) and A23187 (1 similar to 10 mu M) can stimulate the meiotic maturation. In addition, verapamil (1 similar to 100 mu M) and trifluoperazin (10 similar to 1,000 mu M) could inhibit serotonin-induced oocyte maturation. Therefore, Ca2+ is essential for the reinitiation of meiotic maturation in oocytes of the northern quahog. Moreover, an increase i [Ca2+]i can promote meiotic maturation.

高原鼢鼠和高原鼠兔骨骼无机化学成分的研究I.常量元素

本文对高原鼢鼠和高原鼠兔骨骼中的无机常量元素K、N a、Ca���M g、P 和A l 进行了比较分析。研究结果表明, 高原鼢鼠骨骼中Ca���P、A l 的含量极显著地高于高原鼠兔(P < 0.01) ,K 含量高原鼢鼠极显著地低于高原鼠兔(P < 0.001) , N a 和M g 的含量两者间无显著差异(P > 0.05) ; 骨骼各部位元素总量的分布顺序为: 高原鼢鼠下肢骨> 头骨> 脊柱; 高原鼠兔头骨> 下肢骨> 脊柱。15个元素对中, 大部分元素之间线性相关非常显著, 其中高原鼢鼠10对呈显著的线性相关, 高原鼠兔13对呈显著相关。