Entropy-Enthalpy Compensation May Be a Useful Interpretation Tool for Complex Systems Like Protein-DNA Complexes: An Appeal to Experimentalists

@article{Starikov2012EntropyEnthalpyCM,
  title={Entropy-Enthalpy Compensation May Be a Useful Interpretation Tool for Complex Systems Like Protein-DNA Complexes: An Appeal to Experimentalists},
  author={Evgeni B. Starikov and Bengt Nord{\'e}n},
  journal={arXiv: Statistical Mechanics},
  year={2012}
}
In various chemical systems enthalpy-entropy compensation (EEC) is a well-known rule of behavior, although the physical roots of it are still not completely understood. It has been frequently questioned whether EEC is a truly physical phenomenon or a coincidence due to trivial mathematical connections between statistical-mechanical parameters - or even simpler: A phantom effect resulting from the misinterpretation of experimental data. Here, we review EEC from a new standpoint using the notion… 

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References

SHOWING 1-10 OF 38 REFERENCES

Enthalpy-entropy compensation: a phantom or something useful?

TLDR
It is concluded that EEC may be rationalized in terms of hidden but physically real factors implying a Carnot-cycle model in which a micro-phase transition (MPT) plays a crucial role.

Entropy-enthalpy compensation in chemical reactions and adsorption: an exactly solvable model.

  • K. Freed
  • Chemistry
    The journal of physical chemistry. B
  • 2011
TLDR
The general statistical mechanical basis for solvent induced isokinetic/isoequilibrium entropy-enthalpy compensation in chemical reactions and adsorption is provided, understanding that can be used to control of rate processes and binding constants in diverse applications.

Enthalpy-entropy correlations as chemical guides to unravel self-assembly processes.

TLDR
This tutorial Perspective aims at highlighting the current level of non-quantum rationalization of enthalpy-entropy correlations and their chemical consequences on the tuning and on the programming of intermolecular interactions in pure materials, and in diluted solutions.

Multi-excitation entropy: its role in thermodynamics and kinetics

TLDR
Results are presented which support the MEE model as an explanation of MNR and verified predictions of reasonable values of attempt frequencies and cross sections in kinetic processes, which initially appear unreasonable.

Extent of enthalpy–entropy compensation in protein–ligand interactions

The extent of enthalpy–entropy compensation in protein–ligand interactions has long been disputed because negatively correlated enthalpy (ΔH) and entropy (TΔS) changes can arise from constraints

Hydration of lysozyme: the protein-protein interface and the enthalpy-entropy compensation.

TLDR
Sorption calorimetric data on the hydration of lysozyme that confirms the existence of the heterogeneity and the use of the Langmuir equation for the fitting of the initial part of the sorption isotherm of ly sozyme supports the presented approach.

Enthalpy-entropy compensation reveals solvent reorganization as a driving force for supramolecular encapsulation in water.

TLDR
A chiral self-assembled M4L6 host assembly has been shown to be a suitable host for the supramolecular encapsulation of a series of guests in polar solvents, ranging from simple organic ammonium cations to more complex organometallic species, creating highly selective reactivity within the host cavity.

Heat capacity, enthalpy fluctuations, and configurational entropy in broken ergodic systems.

TLDR
It is shown that it is not possible, in general, to calculate the entropy of a glass from heat capacity curves alone, since additional information must be known related to the details of microscopic fluctuations, which serves as experimental and theoretical proof for the nonexistence of residual glass entropy at absolute zero temperature.

Modeling loop entropy.

  • G. Chirikjian
  • Computer Science, Chemistry
    Methods in enzymology
  • 2011

Constraining binding hot spots: NMR and molecular dynamics simulations provide a structural explanation for enthalpy-entropy compensation in SH2-ligand binding.

TLDR
No evidence is found to support the premise that enthalpy-entropy compensation is an inherent property and it is concluded that preorganization of Src SH2 ligand residues involved in binding hot spots may eventuate in suboptimal interactions with the domain.