Mechanism-guided improvements to the single molecule oxidation of carbon nanotube sidewalls.
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.
Coroneus
John G
JG
Department of Molecular Biology and Biochemistry, University of California Irvine, California 92697-2025, USA.
Goldsmith
Brett R
BR
Lamboy
Jorge A
JA
Kane
Alexander A
AA
Collins
Philip G
PG
Weiss
Gregory A
GA
D015374:Biosensing Techniques / Q000295:instrumentation / Q000639:trends; D002264:Carboxylic Acids / Q000737:chemistry; D004553:Electric Conductivity; D004563:Electrochemistry; D004566:Electrodes; D007700:Kinetics; D015394:Molecular Structure; D037742:Nanotubes, Carbon / Q000737:chemistry*; D010084:Oxidation-Reduction; D012666:Semiconductors; D013499:Surface Properties
D002264:Carboxylic Acids; D037742:Nanotubes, Carbon