Structural and Synthetic studies of biologically active natural glycoconjugates and peptides

对具有生物活性的糖缀合物和磷酸肽进行了结构和合成研究，目的是阐明负责其功能的活性结构及其作用机制。细胞因子诱导成分的分离和研究其化学结构的脂磷壁酸馏分革兰氏阳性肠球菌细胞通过多步色谱程序。活性成分被证明是不同于脂多糖或胞壁酰肽的新型糖缀合物，脂多糖或胞壁酰肽是典型的已知的细菌来源的免疫刺激剂。本文还研究了另一种从分枝杆菌细胞中提取的具有相似生物学功能的高分子糖缀合物。通过选择性活化硫苷类化合物，建立了几种高效的方法。其中一些程序得到了有效应用， ...更多信息 内毒素糖复合物的合成工作在吡啶胺化反应的基础上，通过制备双功能荧光试剂，提出了一种新的方法来阐明碳水化合物的功能作用。用这些试剂标记的糖适合于用HPLC纯化，然后可以与高分子基质偶联形成新的糖缀合物，这为生物学研究提供了新的途径。化学合成一种与硫酸化多糖肝素部分结构相对应的硫酸化二糖。合成标本的生物学研究表明，特殊的二糖组分在肝素的血小板结合中起着重要作用。磷酸肽的合成研究对于基本理解蛋白质磷酸化的作用是重要的，现在已知蛋白质磷酸化是生命系统中的一个关键过程。研究了磷酸丝氨酸多肽合成的反应条件、保护基和偶联试剂的组合，建立了适用于固相和液相合成的高效方法。少

Structural and synthetic studies were performed on biologically active glycoconjugates and phosphopeptides for the purpose to elucidate the active structures responsible to their functions and the mechanisms of their action. Cytokine-inducing components were isolated and studied for their chemical structures from the lipoteichoic acid fraction of gram positive enterococcal cells through a multistep chromatographic procedure. The active components proved to be novel glycoconjugates different from lipopolysaccharides or muramyl peptides which are typical known immunostimulants of bacterial origin. Another high molecular glycoconjugate with similar biological functions from mycobacterial cells was also investigated.Stereoselective construction of glycosidic linkages is an essential issue for chemical synthesis of complex glycoconjugates. Several efficient methods for this purpose were established by selective activation of thioglycosides. Some of the procedures were applied effectively to … More our synthetic work on endotoxic glycoconjugates. A novel procedure for elucidation of functional role of carbohydrates was also presented by preparation of bifunctional fluorescent reagents based on the known pyridylamination procedure. Labeled carbohydrates with these reagents are suitable for purification with HPLC and can then be coupled with high molecular matrices to form neo-glycoconjugates, which offers new route for biological investigation.Chemical synthesis of a specific sulfated disaccharide corresponding to a partial structure of sulfated polysaccharide, heparin. Biological study with the synthetic specimen led to the conclusion that the particular disaccharide component plays an important role in platelet binding of heparin.Synthetic study of phosphopeptide is important for basic understanding of the role of protein phosphorylation which is now known to be a crucial process in living systems. Reaction conditions as well as combination of protecting groups and coupling reagents were investigated for the preparation of phosphoserine containing peptides to establish efficient procedures applicable to both solid and liquid phase synthesis. Less