Molecular electrostatic potentials: an effective tool for the elucidation of biochemical phenomena.

Abstract

The electrostatic potential V(r) that is created in the space around a molecule by its nuclei and electrons (treated as static distributions of charge) is a very useful property for analyzing and predicting molecular reactive behavior. It is rigorously defined and can be determined experimentally as well as computationally. The potential has been particularly useful as an indicator of the sites or regions of a molecule to which an approaching electrophile is initially attracted, and it has also been applied successfully to the study of interactions that involve a certain optimum relative orientation of the reactants, such as between a drug and its cellular receptor. A variety of methods for calculating V(r) is available, at different levels of rigor. For large biologically active molecules, multipole expansions and superposition of potentials computed for subunits have been found to be effective. A large number of chemical and biochemical systems and processes have now been studied in terms of electrostatic potentials. Three examples of such applications are surveyed in this paper. These deal with: (a) reactive properties of nucleic acids, including their component bases; (b) biological recognition processes, including drug-receptors and enzyme-substrate interactions; and (c) chemical carcinogenesis, referring specifically to the polycyclic aromatic hydrocarbons and halogenated olefins and their epoxides. For each of these areas, examples of the use of electrostatic potentials in elucidating structure-activity patterns are given.

Can Combined Electrostatic and Polarization Effects Alone Explain the F···F Negative-Negative Bonding in Simple Fluoro-Substituted Benzene Derivatives? A First-Principles Perspective

“…Given that the dimer systems examined comprise several halogen atoms, it is not possible for us to perform reasonably high-level calculations. We thus have employed the standard ab initio second-order Møller-Plesset perturbation theory (MP2) in combination with the molecular electrostatic surface potential (MESP) approach [51] to address these questions above.…”

Sigma-Holes in Battery Materials Using Iso-Electrostatic Potential Surfaces

“…Here, Z A represents charge on nucleus A at position R A . Each term contributes independently for the nuclei and electrons, respectively [27]. Thus, as concluded earlier [28], the electrostatic potential function is a transformation of the electron density and therefore of the wavefunction, containing all information available in both, and with the additional feature of presenting such information in a more suitable way to study interactions between molecules (intermolecular), as well as interactions in molecules (intramolecular).…”

Mononuclear Cr(III), Mn (II), and Fe(III) complexes derived from new ONO symmetrical flexible hydrazone: synthesis, spectral characterization, optical band gap and DFT computational study

“…The molecular structure with its physiochemical property relationship as well as hydrogen bonding interactions can be examined in terms of the MEP (Molecular electrostatic potential) which is a plot of electrostatic potential mapped onto the constant electron density surface [35,36]. The electrostatic potential V(r) at a given point r (x, y, z) is defined in terms of the interaction energy between the electrical charge generated from the molecule electrons, nuclei and proton located at r [37]. In the present study, 3D plots of MEP (Fig12) have been drawn.…”