Construction and Functionalization of Rotaxane and Polyrotaxane Immobilized on Gold Substrate for Molecular Devices

分子器件金基底固定轮烷和聚轮烷的构建及功能化

基本信息

批准号：
21350061
负责人：
KIMURA Shunsaku
金额：
$ 12.81万
依托单位：
Kyoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2009
资助国家：
日本
起止时间：
2009 至 2011
项目状态：
已结题

项目摘要

Various cyclic.-peptides were synthesized as a ring component of rotaxanes. Those cyclic peptides were 1) cyclic tri-.-peptide of cyclo(4-(4-pyridyl)-.-homoalanine) 3, 2) cyclic tri-.-peptide composed of two.-glucosamino acid residues and a trans-2-aminocyclohexylcarboxylic acid residue, 3) cyclic tetra-.-peptide composed of three.-alanine residues and a L-.-homolysine residue having 10, 12-pentacosadiynoic amide at the side chain, 4) cyclic hexa-.-peptide composed of six.-glucosamino acid residues, and 5) cyclic hexa-.-peptides having three glysine residues or three lipoic acids at the side chains. All these cyclic.-peptides were found to form peptide nanotubes under suitable conditions. The peptide nanotube composed of cyclo(4-(4-pyridyl)-.-homoalanine) 3 was subjected to electroless plating to yield a Ni nanotube. The other cyclic tri-.-peptide composed of two.-glucosamino acid residues and a trans-2-aminocyclohexylcarboxylic acid residue formed a bundle of the peptide nanotube with nine columns in a bundle. The cyclic tetra-b-peptide formed a peptide nanotube with extending the 10, 12-pentacosadiynoic amide chain toward the same surface of the nanotube, which allowed polymerization of the diacetylene units along the peptide nanotube. The cyclic hexa-?-peptide took two types of conformations, which became an obstacle to construct the rotaxane structure on gold surface. The experimental conditions for preparation of the rotaxane on gold surface remain to be found out.

合成了各种环状肽作为轮烷的环组分。这些环肽是1)环(4-(4-吡啶基)-.-高丙氨酸)3的环状三-.-肽3, 2)由两个.-葡萄糖氨基酸残基和反式-2组成的环状三-.-肽-氨基环己基羧酸残基，3)由三个.-丙氨酸残基和一个L-.-高赖氨酸残基组成的环状四-.-肽，具有10、侧链具有12-二十五碳二炔酰胺，4)由6个葡萄糖氨基酸残基构成的环状六肽，以及5)侧链具有3个甘氨酸残基或3个硫辛酸的环状六肽。发现所有这些环状肽在合适的条件下形成肽纳米管。对由环(4-(4-吡啶基)-·高丙氨酸) 3 组成的肽纳米管进行化学镀以产生Ni纳米管。另一种环状三肽由两个β-葡萄糖氨基酸残基和一个反式-2-氨基环己基羧酸残基组成，形成一束九柱的肽纳米管。环状四-b-肽形成肽纳米管，其中10, 12-二十五碳二炔酰胺链向纳米管的同一表面延伸，这使得丁二炔单元能够沿着肽纳米管聚合。环状六肽具有两种构象，这成为在金表面构建轮烷结构的障碍。金表面制备轮烷的实验条件仍有待探索。