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耦合纳米机械运动:金属离子效应、pH 值调节、双域螺旋/线性分子链的同时伸缩运动。

Coupled nanomechanical motions: metal-ion-effected, pH-modulated, simultaneous extension/contraction motions of double-domain helical/linear molecular strands.

机构信息

Laboratoire de Chimie Supramoléculaire, Institut de Science et d'Ingénierie Supramoléculaires, Université de Strasbourg , 8 Allée Gaspard Monge, Strasbourg, 67000, France.

出版信息

J Am Chem Soc. 2014 Mar 5;136(9):3400-9. doi: 10.1021/ja408752m. Epub 2014 Feb 18.

DOI:10.1021/ja408752m
PMID:24547897
Abstract

A new class of shape-enforced synthetic polyheterocyclic molecular strands, containing both a helical and a linear domain, has been designed and synthesized. On reaction with Pb(II), under the effect of cation binding to the coordination subunits, the helical section unfolds into a linear shape in the complex and the linear domain folds into a helical ligand wrapped around the bound cations. Such double-domain ligand strands are thus able to undergo a combined unfolding-folding interconversion on binding and release of metal cations. These changes can be modulated through coupling to a competing ligand that reversibly binds and releases metal cations, when respectively unprotonated and protonated, on effecting alternate pH changes. The resulting process thus performs nanomechanical extension/contraction molecular motions of a linear motor type, which is fueled by acid-base neutralization.

摘要

一类新型的受形状约束的合成杂多环分子链已被设计和合成,其中包含一个螺旋和一个线性结构域。在与 Pb(II)反应时,在配位亚基与阳离子结合的影响下,螺旋部分在配合物中展开成线性形状,而线性结构域折叠成螺旋配体,包裹在结合的阳离子周围。因此,这种双结构域配体链能够在结合和解离金属阳离子时进行折叠-展开的协同互变。通过与竞争配体偶联,可以调节这种互变,当竞争配体分别在去质子化和质子化时可逆地结合和解离金属阳离子,通过交替的 pH 变化来实现。因此,这一过程表现出一种由酸碱中和提供动力的线性马达式的纳米机械伸缩分子运动。

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