金属配位超分子晶体的结构特性及在催化氧化裂解壳聚糖中的应用  

The Crystal Structure of Metal Coordination Supermolecular and its using in Catalysis-Oxidation Cleaving Chitosan

作　　者：陈志利[1] 刘军华[1] 张岐[1] 廖代正[2] 王耕霖[2] 卜卫民[3] 

机构地区：[1]海南大学理工学院,海口570228 [2]南开大学化学系,天津300071 [3]吉林大学超分子/光谱实验室,长春130023

出　　处：《无机化学学报》2003年第1期20-24,共5页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金资助项目(No.20061001);国家高技术研究发展专项经费资助。

摘　　要：N,N'-二(2-氨丙基)草酰胺(H2apo)、硫氰酸根与铜?离子在适宜条件下可通过自组装方式形成配合物犤Cu2(apo)(NCS)2犦n,单晶解析结果表明这是一个新型的二维网状结构配位高分子。铜?由反式双三齿配体apo2-和硫氰酸根通过μ2-SCN的方式共同桥连。研究发现该固体在弱酸性溶液中、过氧化氢存在条件下对壳聚糖(一种氨基多糖)具有催化裂解作用。初步的分级分离结果表明降解寡糖分子量大部集中在3000～5000范围。A novel two-dimensional network copper (11) complex bridged by N, N'-bis (2-aminopropyl) oxamide dianion (apo) and thiocyanate [Cu(apo) (NCS)(2)]n has been isolated and characterized by IR, electronic spectra, EPR and X-ray diffraction analysis. The crystal structure belongs to monoclinic, space group P2(1)/c with cell dimensions, a = 7.3131 (14), b = 10.22860(13), c = 11.199(2) Angstrom; beta = 106.63(2); V = 807.2(2) Angstrom(3), Z = 2, F(000) = 452, R-1 = 0.0502, wR(2) = 0.1057. The complex shows a pronounced two-dimensional character developing along the a axis. Within the layer the copper (11) ions are bridged by both apo(2-) and NCS-, the former behaving as a bis (tridentate) ligand in a trans conformation whereas the latter bridges the copper centers in asymmetric end-to-end fashion extending along the be plane to form an infinite network. In this layer, every apo(2-) links four neighbor apo(2-)s by hydrogen bonds. The complex could catalysis-oxidation cleaving chitosan as a matrix with H2O2 presented. This method can narrow the molecular weight distribution.

关 键 词：金属配位 超分子晶体 结构特性 催化氧化 裂解 壳聚糖 铜(Ⅱ)配合物 二维网状配位 晶体结构 壳聚糖降解 

分 类 号：O641.4[理学—物理化学] O614.121[理学—化学]