Todd P. Silverstein · 2024 · The Journal of Physical Chemistry B · ACS Publications · added 2026-04-20
In a recent series of papers, James W. Lee reported that mitochondrial oxidative phosphorylation violates the second law of thermodynamics and that it is allowed to do so because it is a "Type-B" proc Show more
In a recent series of papers, James W. Lee reported that mitochondrial oxidative phosphorylation violates the second law of thermodynamics and that it is allowed to do so because it is a "Type-B" process that features lateral and longitudinal membrane asymmetry. We show here that these contentions are based on problematic interpretations of the literature. More reliable values of ΔGredox and ΔGATP synthesis show that the second law is not violated. More recent reports on the structures of the redox-driven proton pumps (Complexes I, III, and IV) suggest that longitudinal membrane asymmetry does not exist. Finally, Lee's predictions for the concentration of protons localized at the P-side surface of the bioenergetic membrane are likely to be much too high due to several errors; thus, his predicted high values of ΔpHsurface that violate the second law are likely to be wrong. There is currently no strong experimental or theoretical evidence to support the contention that oxidative phosphorylation violates the second law of thermodynamics. Show less
ABSTRACTTo understand the nature of heterogeneous catalytic processes and improve their efficiency, it is necessary to conduct both experimental and theoretical studies. At the same time, there is no Show more
ABSTRACTTo understand the nature of heterogeneous catalytic processes and improve their efficiency, it is necessary to conduct both experimental and theoretical studies. At the same time, there is no unified approach to obtaining the necessary data using quantum chemistry methods. In this work, problems of the existing calculational approaches are analyzed. The obtained information is used to develop the original three‐layer embedded cluster model approach, which is shown to be the most effective. The general algorithm for obtaining such models for various oxides is formulated. The sufficient accuracy of the proposed models in predicting geometric and energy characteristics, vibrational frequencies, activation barriers, and thermodynamic characteristics is verified. The specifics of calculating the thermodynamic characteristics of heterogeneous processes using the proposed cluster models is studied in detail. The developed approach is an effective tool for studying the mechanism of heterogeneous catalytic processes both by itself and in combination with experiment. Show less