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Cosolvent Dimethyl Sulfoxide Influences Protein–Ligand Binding Kinetics via Solvent Viscosity Effects: Revealing the Success Rate of Complex Formation Following Diffusive Protein–Ligand Encounter

Sven Wernersson, Simon Birgersson, Mikael Akke

2022Biochemistry13 citationsDOIOpen Access PDF

Abstract

N NMR relaxation to monitor kinetics. The binding enthalpy is not affected, but we observe a subtle trend of increasingly unfavorable entropy of binding, and consequently decreased affinity, with increasing DMSO concentration. The increasing concentration of DMSO results in a reduced association rate of binding, while the dissociation rate is less affected. The observed association rate is inversely proportional to the viscosity of the DMSO-water mixture, as expected from theory, but significantly reduced from the diffusion-controlled limit. By comparing the viscosity dependence of the observed association rate with that of the theoretical diffusion-controlled association rate, we estimate the success rate of productive complex formation following an initial encounter of proteins and ligands, showing that only one out of several hundred binding "attempts" are successful.

Topics & Concepts

ChemistryIsothermal titration calorimetryKineticsLigand (biochemistry)Dimethyl sulfoxideSolventTitrationDissociation (chemistry)Aqueous solutionEntropy of activationReceptor–ligand kineticsReaction rate constantPhysical chemistryOrganic chemistryBiochemistryReceptorPhysicsQuantum mechanicsGalectins and Cancer BiologyToxin Mechanisms and Immunotoxinsthermodynamics and calorimetric analyses