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Terai, Kiriko

Publications and source records attributed to Terai, Kiriko.

Correlated particle transport enables biological free energy transduction

Studies of biological transport frequently neglect the explicit statistical correlations among particle site occupancies (i.e., they use a mean-field approximation). Neglecting correlations sometimes captures biological function, even for out-of-equilibrium and interacting systems. Here, we show that neglecting correlations fails to describe free energy transduction, mistakenly predicting an abundance of slippage and energy dissipation, even for networks that are near reversible and lack interactions among particle sites. Interestingly, linear charge transport chains are well described without including correlations, even for networks that are driven and include site-site interactions typical of biological electron transfer chains. We examine three specific bioenergetic networks: a linear electron transfer chain (as found in bacterial nanowires), a near-reversible electron bifurcation network (as in complex III of respiration and other recently discovered structures), and a redox-coupled proton pump (as in complex IV of respiration).

bacterial nanowires↗

Efficient and reversible electron bifurcation with either normal or inverted potentials at the bifurcating cofactor

A longstanding mystery surrounding electron bifurcation is the significance of inverted (or “crossed”) reduction potentials of the two-electron bifurcating cofactor. Using a many-electron open-system kinetic model, we show that reversible and efficient electron bifurcation is possible without inverted reduction potentials at the bifurcating site if the absolute value of the difference between first and second reduction potentials of the bifurcating species is sufficiently large (on the scale of the redox-potential span of the high- and low-potential branches). Surprisingly, the case with strong, normally ordered potentials at the bifurcating cofactor can produce electron bifurcation that is just as effective as the case with strongly inverted potentials. Lastly, this finding amplifies the puzzle surrounding the recruitment of inverted potentials in the few well-characterized bifurcating systems of nature and suggests that electron bifurcating cofactors without strongly inverted potentials may yet be discovered.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗