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

合成了多种环肽作为轮烷的环组分。这些环肽是1)环(4-(4-吡啶)-高丙氨酸)的环三肽，2)由两个氨基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的环三肽，3)由三个丙氨酸残基和一个L-高氨酸残基组成的环四肽，4)由六个氨基二糖氨基酸残基组成的环六肽，以及5)在侧链具有三个甘氨酸残基或三个脂酸残基的环六肽。所有这些环肽都在合适的条件下形成了多肽纳米管。由环(4-(4-吡啶)-高丙氨酸)3组成的多肽纳米管被化学镀成镍纳米管。另一个由两个-氨基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的环状三-肽形成了一束具有9根柱子的多肽纳米管束。环状四b-肽通过向纳米管的同一表面延伸10，12-五二羟基酰胺链形成了多肽纳米管，这使得二乙炔单元可以沿着多肽纳米管聚合。环状六肽以两种构象存在，阻碍了轮烷在金表面的构筑。在金表面制备轮烷的实验条件有待进一步研究。

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.