Proton transfer dynamics dictate quinone speciation at lipid-modified electrodes

Literature Information

Publication Date 2017-02-10
DOI 10.1039/C6CP07586J
Impact Factor 3.676
Authors

Edmund C. M. Tse, Christopher J. Barile, Ying Li, Steven C. Zimmerman, Ali Hosseini


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Abstract

Proton-coupled electron transfer (PCET) reactions are ubiquitous in biochemistry and alternative energy schemes. Natural enzymes utilize quinones in proton transfer chains and energy conversion processes. Here, we utilize a bio-inspired hybrid bilayer membrane system to control the reaction mechanism of a quinone molecule covalently bound to an electrode surface. In particular, by impeding proton access to the quinone moiety, we change the reaction pathway from a PCET process to a pure electron transfer step. We further alter the reaction pathway to a stepwise PCET process by controlling the proton flux through the use of an alkyl proton carrier incorporated in the lipid membrane. By modulating proton availability, we control the quinone reaction pathway without changing the molecular structure of the redox species. This work provides unique insight into PCET reactions and a novel electrochemical platform for interrogating them.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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