Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603 (Japan) http://helix.mol.nagoya-u.ac.jp/
Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603 (Japan) http://helix.mol.nagoya-u.ac.jp/.
Angew Chem Int Ed Engl. 2015 Nov 23;54(48):14442-6. doi: 10.1002/anie.201507918. Epub 2015 Oct 1.
The dynamic planar chirality in a peptide-bound Ni(II)-salphen-based macrocycle can be remotely controlled. First, a right-handed (P)-3(10)-helix is induced in the dynamic helical oligopeptides by a chiral amino acid residue far from the macrocyclic framework. The induced planar chirality remains dynamic in chloroform and acetonitrile, but is almost completely locked in fluoroalcohols as a result of the solvent-induced transition of the peptide chains from a 3(10)-helix to a wider α-helix, which freezes the rotation of the pendant peptide units around the macrocycle.
在与肽键合的 Ni(II)-salphen 基大环中，可以远程控制动态平面手性。首先，在远离大环骨架的手性氨基酸残基的作用下，动态螺旋寡肽中诱导出右手（P）-3(10)-螺旋。在氯仿和乙腈中，诱导的平面手性仍然是动态的，但由于肽链从 3(10)-螺旋向更宽的 α-螺旋的溶剂诱导转变，在氟醇中几乎完全被锁定，这使得侧挂肽单元围绕大环的旋转被冻结。
