糖蛋白/胆红素钙水溶性复合物的形成及光谱研究

采用傅立叶变换红外光谱(FT-IR)，结合减法、二阶导、退卷积和曲线拟合等先进光谱技术，紫外可见光谱，ICP-AES分析方法，对不同质量比的α-酸性糖蛋白(AGP)和胆红素钙(CaBR)反应后的滤液进行了研究。结果表明，AGP和CaBR之间存在着较强的相互作用，导致AGP二级结构的有序性增加，CaBR的水溶性增大，两者形成了可溶性的AGP/CaBR复合物。     

Dicopper(I) oxalate complexes as molecular precursors for the deposition of copper compounds

The synthesis, characterization, and thermal decomposition behavior of dicopper(I) oxalato complexes L₄Cu₂(C₂O₄) (L = CNtBu (2a), CNCMe₂CH₂tBu (2b), CNC₆H₃Me₂-2,6 (2c)) is reported. 2c can be prepared in a straightforward manner by the reaction of stoichiometric amounts of Cu₂O and oxalic acid with four equivalents of CNC₆H₃Me₂-2,6, while those complexes with aliphatic isocyanides are better prepared from a copper(I) oxalato complex with alkine capping ligands (Me₃SiCCSiMe₃)₂Cu₂(C₂O₄) (1) via ligand exchange. Crystallographic and spectroscopic evidence for 2a-c confirms the anticipated dinuclear structure with the oxalate in a μ-1,2,3,4 bridging mode and an essentially σ-character of the terminal isocyanides. In solid form the complexes are stable at room temperature and can be handled in air for some time. Their decomposition was studied by thermal gravimetric analysis coupled with mass spectrometry, and the degradation pathway was shown to depend on the type of isocyanide capping ligand. Decomposition of 2a,b takes place between 150 and 200 °C to give CuCN in a clean process that involves isobutene elimination from the terminal ligands, with elimination of (CN)₂ and conversion to elemental copper at higher temperatures. Heating of 2c leads to CuO (and then to Cu₂O) via release of the intact isocyanide, CO₂, and CO in a well-behaved thermal process around 200-280 °C.     

新型稀土芳香羧酸类配合物的合成及其光致和电致发光性质

合成了新型可溶性稀土芳香羧酸类配合物，测定了有机配体的三重态能级，并考察了其光致发光相对强度、荧光寿命，发现该系列稀土配合物具有很高的光致发光效率。利用其优良的溶解性，采用高聚物掺杂、旋涂技术将其制成薄膜应用于电致发光研究中，成功地制备出具有高色纯度的稀土有机电致发光器件。对于ITO／PVK／PVK：Tb(AS)3Phen：PBD／PBD／Al电致发光器件，其最大亮度为32cd．m^-2。     

First example of the formation of bipolar spiro σ-complexes from 6-bromo-5,7-dinitrobenzo[e]-1,2,3,4-tetrazine 1,3-di-N-oxide

The reactions of 3,5,7-trimethyltropolone and 2-(N-benzylamino)tropone with 6-bromo-5,7-dinitrobenzo[e]-1,2,3,4-tetrazine 1,3-di-N-oxide afforded novel bipolar spiro -complexes. The kinetic and activation parameters of the R,S-enantiotopomerization of a chiral spiro -complex of 2-(N-benzylamino)tropone were determined using dynamic ¹H NMR spectroscopy.     

乙烯系单体自由基聚合的阻聚效应——Ⅸ.受阻胺-醌类电荷转移络合物对甲基丙烯酸甲酯自由基聚合的阻聚及历程

用膨胀计法研究了西氯苯醌(CA)、苯醌(BQ)与受阻胺二异丙胺(DIPA)、2,2,6,6-四甲基-4-羟基哌啶(TMP)形成的电荷转移络合物(CTC)对偶氮二异丁腈(AIBN)引发的甲基丙烯酸甲酯(MMA)自由基聚合阻聚效应。结果表明,CA-DIPA、CA-TMP、BQ-DIPA和BQ-TMP对MMA的自由基聚合均产生较单独的醌或胺更显著的阻聚能力。其中以CA-DIPA阻聚效果更佳。比较了MMA在苯或乙腈中的溶液聚合,得类似结果。初步讨论了受阻胺-醌电荷转移络合物对MMA自由基聚合的阻聚反应机理。     

微乳液法制备超细K2Ln2Ti3O10及其光催化活性研究

以钛酸四丁酯、氢氧化钾和镧系金属氧化物为原料。采用微乳液法制备了系列超细K2Ln2Ti3O10（Ln=La．Ce,Pr．Nd，Sm，Eu，Gd）光催化剂。并考察了其光催化活性。通过X射线衍射（XRD）、透射电镜（TEM）和紫外可见吸收光谱（UV—Vis）对其进行了表征。结果表明：用微乳液法制备催化剂可以在较低的温度下（900℃），用较短的烧结时间（3h）合成结晶度高、粒径较小（200Mm）的K2Ln2Ti3O10钙钛矿型层状结构化合物。催化剂在紫外光和可见光条件下均具有光催化降解甲基橙的活性。紫外光条件下可以明显提高光催化降解活性，降解率达到60％。     

The preparation of nano‐scope chitosan‐oligomer copper complexes and their interaction with DNA

Water‐soluble low molecular weight chitosan of nanometer level and its copper complexes were prepared, and characterized by IR spectra, elemental analysis and gel permeation chromatography (GPC). The modes and mechanism of these copper complexes interaction with DNA were studied by a fluorescent probe method and electrophoresis analysis. It is suggested that there are electrostatic and intercalation modes of copper complexes interacting with DNA. At first, the cationic complex electrostaticly binds to the negatively charged phosphate backbone of DNA, and then a portion of the complex intercalates between the base pairs on the DNA duplex strand. Copyright © 2005 John Wiley & Sons, Ltd.     

非螯合型手性双膦铑对脱氢苯丙氨酸的不对称催化加氢反应

报道从Ｄ－甘露醇出发合成手性双膦（２Ｓ，５Ｓ）－３，６－双（二苯膦）－１，４：３，６－双脱水－２，５－双去氧－Ｌ－艾杜醇，原位下ＢＤＰＩ与３种铑配合物作用生成手性非螯合型双膦铑催化剂，常压下对４种脱氢苯丙氨酸衍生物进行不对称催化化反主尖，对反应结果及ｅ．ｅ．值进行了讨论。