Revealing a nonergodic mechanistic pattern for electron exchange between azurin and electrodes coated by nano-films under the glassy environmental conditions
Dolidze T, van Eldik R, Khoshtariya D (2019)
Publication Type: Journal article
Publication year: 2019
Journal
Book Volume: 13
Pages Range: 97-103
Journal Issue: 4
Abstract
Fast-scan protein-film voltammetry was applied to explore interfacial biomimetic electron exchange under the environmental glass forming conditions. Gold electrodes were coated with 1-pentanethiol SAM–azurin (Az, blue cupredoxin) assemblies and placed in contact with a water-doped and buffered protic ionic melts of choline dihydrogen phosphate ([ch][dhp]), served as electrolyte media, allowing for a necessary cell conductivity under the virtually solid, semi-solid and liquid electrolyte conditions over 273–353 K, within which the electron exchange rate was studied as a function of the water amount and temperature. Exposure of the Az films to the semi-solid electrolyte greatly affected the protein’s conformational dynamics, hence the ET rate, via the mechanism occurring in the extra complicated dynamically-controlled regime. Results are compared to the earlier studies on the reference system with a conventional electrolyte, allowing for the disclosure of mutually-entangled mechanistic motifs. Under the “standard” condition (with no [ch][dhp] added), the Az biomolecule may reside in an apparently ergodic state, whereas upon adding of [ch][dhp] to allow water content ranging between 6 to 15 waters per [ch][dhp], system displays anomalous temperature dependences, suggesting that the reactive system crosses a broad, well-manifested nonergodic zone which arises from the continuous interplay (freezing/unfreezing) of ET-coupled highly cooperative conformational modes of the Az protein, inherently linked to the electrolyte’s slowest collective relaxation(s). Above this [ch][dhp] concentration, allowing the water content between 1.65 to 3.7 waters per ion pair, the system returns to a series of new, quasi-ergodic states, with each displaying virtually linear Arrhenius patterns yet with distinct parameters.
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Georgia (GE)How to cite
APA:
Dolidze, T., van Eldik, R., & Khoshtariya, D. (2019). Revealing a nonergodic mechanistic pattern for electron exchange between azurin and electrodes coated by nano-films under the glassy environmental conditions. Bulletin of the Georgian National Academy of Sciences, 13(4), 97-103.
MLA:
Dolidze, Tinatin, Rudi van Eldik, and Dimitri Khoshtariya. "Revealing a nonergodic mechanistic pattern for electron exchange between azurin and electrodes coated by nano-films under the glassy environmental conditions." Bulletin of the Georgian National Academy of Sciences 13.4 (2019): 97-103.
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