Thermodynamically Consistent Coarse Graining of Biocatalysts beyond Michaelis--Menten

Starting from the detailed catalytic mechanism of a biocatalyst we provide a coarse-graining procedure which, by construction, is thermodynamically consistent. Œis procedure provides stoichiometries, reaction ƒuxes (rate laws), and reaction forces (Gibbs energies of reaction) for the coarse-grained level. It can treat active transporters and molecular machines, and thus extends the applicability of ideas that originated in enzyme kinetics. Moreover, we identify the conditions under which a relation between ƒuxes and forces holds at the coarse-grained level as it holds at the detailed level. In doing so, we clarify the speculations and broad claims made in the literature about such a general ƒux–force relation.