Journal
POLYMER
Volume 47, Issue 7, Pages 2483-2492Publisher
ELSEVIER SCI LTD
DOI: 10.1016/j.polymer.2005.12.091
Keywords
atomic force microscopy; electrochemistry; stimuli-responsive polymer
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We investigated various stimuli-responsive poly(ferrocenylsilane) (PFS) polymers as model systems for the realization of molecular motors powered by a redox process. Covalently end-grafted PFS on gold, as well as PFS homopolymers and block copolymers in ultrathin films, were studied by AFM-based single molecule force spectroscopy (SMFS). Surface confined PFS macromolecules were chemically oxidized by addition of tetracyanoethylene or were completely and reversibly oxidized (and reduced) in situ by applying an electrochemical potential. Chemical oxidation was successful only for the block copolymers. The entropic elasticity of neutral PFS chains (Kuhn length I-K similar to 0.40 nm) was found to be larger than that of oxidized PFS chains (I-K similar to 0.65 nm) in the lower force regime. The elasticities could be reversibly controlled in situ by adjusting the applied potential in electrochemical SMFS experiments. For a single PFS macromolecule (DP = 80) operating cycle, a work output and an efficiency of 3.4 X 10(-19) J and similar to 5%, respectively, were estimated based on the single chain experimental data. (c) 2006 Elsevier Ltd. All rights reserved.
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