Enthalpy-entropy compensation (EEC) is observed in diverse molecular binding processes of importance to living systems and manufacturing applications, but this widely occurring phenomenon is not sufficiently understood from a molecular physics standpoint. To gain insight into this fundamental problem, we focus on the melting of double-stranded DNA (dsDNA) since measurements exhibiting EEC are e...

The mechanism and thermodynamic functions of the self-assembly of a family of covalently linked oligomeric naphthalenediimides (NDIs) were investigated through variable-temperature NMR and CD studies. The NDIs were shown to self-assemble into helical supramolecular nanotubes via an isodesmic polymerisation mechanism, and regardless of the oligomer length a surprising entropy-enthalpy compensati...

The concept of entropy–enthalpy compensation has exercised a peculiar fascination for biochemists since it was first proposed.[1, 2] The idea is that if a particular rate constant or equation constant is measured for a series of sample of the same enzyme from different sources, the variations in enthalpies of activation or of reaction will largely cancelled out by variations in the correspondin...

We review here the well-known but still hotly debated notion of entropy-enthalpy compensation (EEC) from an unconventional standpoint: in terms of correlation. Specifically, correlation could mean either that ‘A’ is correlated to ‘B’ due to that ‘A’ directly results from ‘B’, or vice versa, or that there may be some real, but hidden ‘C’ connected to both ‘A’ and ‘B’. In accordance with the seco...

A statistical mechanical theory is presented to predict the effects of macromolecular crowding on protein association equilibria, accounting for both excluded volume and attractive interactions between proteins and crowding molecules. Predicted binding free energies are in excellent agreement with simulation data over a wide range of crowder sizes and packing fractions. It is shown that attract...