A synthetic small molecule that can walk down a track.

Although chemists have made small-molecule rotary motors, to date there have been no reports of small-molecule linear motors. Here we describe the synthesis and operation of a 21-atom two-legged molecular unit that is able to walk up and down a four-foothold molecular track. High processivity is conferred by designing the track-binding interactions of the two feet to be labile under different sets of conditions such that each foot can act as a temporarily fixed pivot for the other. The walker randomly and processively takes zero or one step along the track using a 'passing-leg' gait each time the environment is switched between acid and base. Replacing the basic step with a redox-mediated, disulfide-exchange reaction directionally transports the bipedal molecules away from the minimum-energy distribution by a Brownian ratchet mechanism. The ultimate goal of such studies is to produce artificial, linear molecular motors that move directionally along polymeric tracks to transport cargoes and perform tasks in a manner reminiscent of biological motor proteins.

[1]  Sijbren Otto,et al.  Orthogonal or simultaneous use of disulfide and hydrazone exchange in dynamic covalent chemistry in aqueous solution. , 2008, Chemical communications.

[2]  Euan R. Kay,et al.  A molecular information ratchet , 2007, Nature.

[3]  Kazuhiko Kinosita,et al.  Direct observation of the rotation of F1-ATPase , 1997, Nature.

[4]  R. Furlan,et al.  Covalent double level dynamic combinatorial libraries: selectively addressable exchange processes. , 2008, Chemical communications.

[5]  T. Aida,et al.  Mechanical twisting of a guest by a photoresponsive host , 2006, Nature.

[6]  P. Yin,et al.  A DNAzyme that walks processively and autonomously along a one-dimensional track. , 2005, Angewandte Chemie.

[7]  I. Derényi,et al.  Fluctuation driven transport and models of molecular motors and pumps , 1998, European Biophysics Journal.

[8]  A. Turberfield,et al.  Coordinated chemomechanical cycles: a mechanism for autonomous molecular motion. , 2008, Physical review letters.

[9]  R. Astumian Design principles for Brownian molecular machines: how to swim in molasses and walk in a hurricane. , 2007, Physical chemistry chemical physics : PCCP.

[10]  Ruojie Sha,et al.  A Bipedal DNA Brownian Motor with Coordinated Legs , 2009, Science.

[11]  Ben L. Feringa,et al.  Unidirectional molecular motor on a gold surface , 2005, Nature.

[12]  Michael M. Pollard,et al.  A Reversible, Unidirectional Molecular Rotary Motor Driven by Chemical Energy , 2005, Science.

[13]  Richard A. Silva,et al.  Unidirectional rotary motion in a molecular system , 1999, Nature.

[14]  Jeremy K. M. Sanders,et al.  Dynamic Combinatorial Libraries of Macrocyclic Disulfides in Water , 2000 .

[15]  Laurent Vial,et al.  Dynamic combinatorial chemistry. , 2006, Chemical reviews.

[16]  Darko Stefanovic,et al.  Behavior of polycatalytic assemblies in a substrate-displaying matrix. , 2006, Journal of the American Chemical Society.

[17]  A V Eliseev,et al.  Double-level "orthogonal" dynamic combinatorial libraries on transition metal template. , 2001, Proceedings of the National Academy of Sciences of the United States of America.

[18]  Toshio Yanagida,et al.  Direct observation of single kinesin molecules moving along microtubules , 1996, Nature.

[19]  Belén Ferrer,et al.  Autonomous artificial nanomotor powered by sunlight , 2006, Proceedings of the National Academy of Sciences of the United States of America.

[20]  Francesco Zerbetto,et al.  Synthetic molecular motors and mechanical machines. , 2007, Angewandte Chemie.

[21]  J. Reif,et al.  A unidirectional DNA walker that moves autonomously along a track. , 2004, Angewandte Chemie.

[22]  Jean-Marie Lehn,et al.  From supramolecular chemistry towards constitutional dynamic chemistry and adaptive chemistry. , 2007, Chemical Society reviews.

[23]  Alan E. Rowan,et al.  Epoxidation of polybutadiene by a topologically linked catalyst , 2003, Nature.

[24]  Stuart J Rowan,et al.  Dynamic covalent chemistry. , 2002, Angewandte Chemie.

[25]  N. Harada,et al.  Light-driven monodirectional molecular rotor , 2022 .

[26]  Harry M. T. Choi,et al.  Programming biomolecular self-assembly pathways , 2008, Nature.

[27]  N. Seeman,et al.  A precisely controlled DNA biped walking device , 2004 .

[28]  Ronald D Vale,et al.  The Directional Preference of Kinesin Motors Is Specified by an Element outside of the Motor Catalytic Domain , 1997, Cell.

[29]  N. Pierce,et al.  A synthetic DNA walker for molecular transport. , 2004, Journal of the American Chemical Society.

[30]  Francesco Zerbetto,et al.  Unidirectional rotation in a mechanically interlocked molecular rotor , 2003, Nature.