Enthalpy-entropy compensation of atomic diffusion originates from softening of low frequency phonons

A fundamental view of enthalpy–entropy compensation

Entropy–enthalpy compensation as deduced from measurements of temperature dependence

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...

Entropy-enthalpy compensation: fact or artifact?

The phenomenon of entropy-enthalpy (S-H) compensation is widely invoked as an explanatory principle in thermodynamic analyses of proteins, ligands, and nucleic acids. It has been suggested that this compensation is an intrinsic property of either complex, fluctuating, or aqueous systems. The questions examined here are whether the observed compensation is extra-thermodynamic (i.e., reflects any...

Enthalpy-entropy compensation at play in human copper ion transfer

Copper (Cu) is an essential trace element but toxic in free form. After cell uptake, Cu is transferred, via direct protein-protein interactions, from the chaperone Atox1 to the Wilson disease protein (WD) for incorporation into Cu-dependent enzymes. Cu binds to a conserved C(1)XXC(2) motif in the chaperone as well as in each of the cytoplasmic metal-binding domains of WD. Here, we dissect mecha...

Entropy-enthalpy Compensation Conformational Fluctuation and Induced--t

A localized change in a protein, which occurs as a result of either ligand binding or single amino acid substitution, necessarily encounters the conformational uctuation of the rest of the protein. Both the entropy and the enthalpy associated with the change consist of contributions from uctuations in the atoms surrounding the localized site, but they compensate. A novel thermodynamic ensemble ...