Understanding the Chemistry of Lead at a Molecular Level: The Pb(II) 6s6p Lone Pair Can Be Bisdirected in Proteins
| Autor: | Ulf Ryde, Olivier Parisel, Jean-Philip Piquernal, Marie-Celine Van Severen |
|---|---|
| Přispěvatelé: | Synthèse Organique Sélective et Chimie Organométallique (SOSCO), Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine-ESCOM-Centre National de la Recherche Scientifique (CNRS), Lund University [Lund], Laboratoire de chimie théorique (LCT), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Lund University [Lund, Sweden] |
| Jazyk: | angličtina |
| Rok vydání: | 2013 |
| Předmět: |
chemistry.chemical_classification
Electron pair 010304 chemical physics Double bond Steric number Nanotechnology 010402 general chemistry 01 natural sciences 0104 chemical sciences 3. Good health Computer Science Applications [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Crystallography Molecular level chemistry 0103 physical sciences Theoretical chemistry [CHIM]Chemical Sciences Physical and Theoretical Chemistry Theoretical Chemistry Lone pair ComputingMilieux_MISCELLANEOUS |
| Zdroj: | Journal of Chemical Theory and Computation Journal of Chemical Theory and Computation, 2013, 9 (5), pp.2416-2424. ⟨10.1021/ct300524v⟩ Journal of Chemical Theory and Computation; 9(5), pp 2416-2424 (2013) Journal of Chemical Theory and Computation, American Chemical Society, 2013, 9 (5), pp.2416-2424. ⟨10.1021/ct300524v⟩ |
| ISSN: | 1549-9618 1549-9626 |
| DOI: | 10.1021/ct300524v⟩ |
| Popis: | Pb(2+) complexes can attain several different topologies, depending of the shape of the Pb 6s6p lone pair. In this paper, we study structures with a bisdirected Pb lone pair with quantum mechanics (DFT) and QM/MM calculations. We study small symmetric Pb(2+) models to see what factors are needed to get a bisdirected lone pair. Two important mechanisms have been found: First, the repulsion of the lone pair of Pb(2+) with other lone pairs in the equatorial plane leads to a bisdirected structure. Second, a bisdirected lone pair can also arise due to interactions with double bonds, lone pairs, or hydrogen atoms. Moreover, we have analyzed Pb(2+) sites in proteins and to see if a bisdirected lone pair can exist in an asymmetrical environment. Several instances of bisdirected lone pairs were discovered. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|