Mechanistic regimes for electron transfer at bio–nano interfaces
- 1School of Pharmacy
- 2University of Nottingham
Abstract
Bioelectronic medicine increasingly operates at interfaces whose dimensions approach redox molecules, electrical double layers and structured electronic states. The central problem is therefore not to identify a size at which electrochemistry becomes quantum, but to determine which physical description explains a response. This challenge is acute for nanoscale bipolar electrodes, where conductor-scale potentials predicted from uniform-field models can be extremely small despite faradaic and biological activity. Local field concentration, double-layer overlap, ion-concentration polarisation, altered reorganisation energetics, stochastic molecular dynamics and electron tunnelling offer coexisting explanations. We propose a falsifiable framework that distinguishes continuum/device, interfacial/cellular, stochastic/few-molecule and quantum-informed regimes by perturbing local potential, field and length, molecular coupling, confinement and electronic structure. Quantum capacitance, bipolar electrochemistry, tunnelling junctions, activationless electron transfer and multiscale modelling illustrate these tests. Size determines when effects may become important; mechanism must be assigned from discriminating behaviour, not from size or endpoint response alone.
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BibTeX
@misc{neethipathi2026mechanistic,
title = {{Mechanistic regimes for electron transfer at bio–nano interfaces}},
author = {Deepan Kumar Neethipathi and Frankie J. Rawson},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15009117/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009117/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Mechanistic regimes for electron transfer at bio–nano interfaces
AU - Deepan Kumar Neethipathi
AU - Frankie J. Rawson
PY - 2026
DA - 2026/09/20
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009117/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009117/v1
AB - Bioelectronic medicine increasingly operates at interfaces whose dimensions approach redox molecules, electrical double layers and structured electronic states. The central problem is therefore not to identify a size at which electrochemistry becomes quantum, but to determine which physical description explains a response. This challenge is acute for nanoscale bipolar electrodes, where conductor-scale potentials predicted from uniform-field models can be extremely small despite faradaic and biological activity. Local field concentration, double-layer overlap, ion-concentration polarisation, altered reorganisation energetics, stochastic molecular dynamics and electron tunnelling offer coexisting explanations. We propose a falsifiable framework that distinguishes continuum/device, interfacial/cellular, stochastic/few-molecule and quantum-informed regimes by perturbing local potential, field and length, molecular coupling, confinement and electronic structure. Quantum capacitance, bipolar electrochemistry, tunnelling junctions, activationless electron transfer and multiscale modelling illustrate these tests. Size determines when effects may become important; mechanism must be assigned from discriminating behaviour, not from size or endpoint response alone.
ER -