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Mechanism‐Guided Improvements to the Single Molecule Oxidation of Carbon Nanotube Sidewalls
Authors:John G Coroneus  Brett R Goldsmith  Jorge A Lamboy  Alexander A Kane  Philip G Collins Prof  Gregory A Weiss Prof
Institution:1. Department of Molecular Biology and Biochemistry, University of California Irvine, California 92697‐2025, USA, Fax: (+1)?949‐824‐9920);2. Department of Physics and Astronomy, University of California, Irvine, California 92697‐2025, USA, Fax: (+1)?949‐824‐2174;3. Department of Chemistry, University of California, Irvine, California 92697‐2025, USA
Abstract:Real‐time monitoring of carbon nanotube conductance during electrochemical and chemical etching reveals the electronic signatures of individual bond alteration events on the nanotube sidewall. Tracking the conductance of multiple single‐molecule experiments through different synthetic protocols supports putative mechanisms for sidewall derivatization. Insights gained from these mechanistic observations imply the formation of sidewall carboxylates, which are useful as handles for bioconjugation. We describe an electronic state required for efficacious chemical treatment. Such real‐time monitoring can improve carboxylate yields to 45 % or more. The experiments illustrate the power of molecular nanocircuits to uncover and direct the mechanisms of chemical reactions.
Keywords:bioconjugation  molecular electronics  nanotubes  oxidation  single‐molecule studies
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