Affordable Access

deepdyve-link
Publisher Website

A Doubly Kinetically-Gated Information Ratchet Autonomously Driven by Carbodiimide Hydration.

Authors
  • Borsley, Stefan1
  • Leigh, David A1
  • Roberts, Benjamin M W1
  • 1 Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, United Kingdom. , (United Kingdom)
Type
Published Article
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society
Publication Date
Mar 11, 2021
Identifiers
DOI: 10.1021/jacs.1c01172
PMID: 33705123
Source
Medline
Language
English
License
Unknown

Abstract

We report a rotaxane-based information ratchet in which the macrocycle distribution is pumped away from equilibrium using a carbodiimide fuel. A carboxylate group on the axle, nonequidistant between two macrocycle binding sites, efficiently catalyzes the hydration of a carbodiimide fuel to the corresponding urea waste, with >80% of the fuel molecules reacting through the machine-catalyzed pathway. The energy of the reaction is harnessed by kinetic differentiation of the mechanical states of the machine driving the macrocycle to the binding site distal to the catalyst. Steric hindrance between the macrocycle and the fuel slows the reaction of the carboxylate group (to form a barrier to macrocycle movement) in the proximal co-conformer, whereas hydrogen bonding between the macrocycle and the barrier accelerates hydrolysis of the activated ester proximal isomer. The two directionally biased processes reinforce each other's effect, resulting in a doubly kinetically gated ratchet that achieves 1:18 directionality, an exceptional degree of selectivity for a synthetic chemically fueled molecular motor.

Report this publication

Statistics

Seen <100 times