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Recovering biological electron transfer reaction parameters from multiple protein film voltammetric techniques informed by Bayesian inference.
- Source :
-
Journal of Electroanalytical Chemistry . Apr2023, Vol. 935, pN.PAG-N.PAG. 1p. - Publication Year :
- 2023
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Abstract
- [Display omitted] • Fitting voltammetry data with large background currents is complicated by local minima. • Showcase the need for multiple experiments to identify the global minimum. • Propose a framework for rapid and reproducible parameter inference for protein film voltammetry experiments. • Bayesian inference provided a powerful insight into the degree of correlation between model parameters. Deciphering the mechanism, kinetics and energetics of biological electron-transfer reactions requires a robust, rapid and reproducible protein-film voltammetry information recovery process. Here we describe a semi-automated computational approach for inferring the chemical reaction parameters for a simple protein system, a bacterial cytochrome domain from Cellvibrio japonicus that displays reversible one-electron Fe 2 + / 3 + redox chemistry. Despite the relative simplicity of the experimental system, developing a robust data analysis approach to find the global optimum in 13-dimensional parameter space is a challenging task because the Faradaic-to-background current ratio in such experiments is often low. We describe how a multiple-technique approach, whereby data from three voltammetry techniques (direct-current, pure sinusoidal and Fourier transform alternating current voltammetry) is combined, ultimately enables the automatic extraction of both (i) quantitative "best-fit" redox reaction parameter point values that are robust across multiple experiments performed on different protein-electrode films, and (ii) a statistical description of parameter correlation relationships, along with uncertainty in the individual parameter values, obtained using Bayesian inference. It is the latter achievement which is particularly important as it represents a method for visualising the possible limitations in the mathematical model of the experimental system. Our multi-voltammetry analysis approach enables such powerful insight because of the complementarity between the information content, simulation-speed and parameter sensitivity of the current–time data generated by the different techniques, illustrating the value of adding purely sinusoidal voltammetry to the bioelectrochemistry measurement toolkit. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 15726657
- Volume :
- 935
- Database :
- Academic Search Index
- Journal :
- Journal of Electroanalytical Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 162891581
- Full Text :
- https://doi.org/10.1016/j.jelechem.2023.117264