title: Remote position substituents as modulators of conformational and reactive properties of quinones. Relevance of the pi/pi intramolecular interaction.
abstract: Several studies have described that quinoid rings with electron-rich olefins at remote position experience changes in their redox potential. Since the original description of these changes, different approaches have been developed to describe the properties of the binding sites of ubiquinones. The origin of this phenomenon has been attributed to lateral chain flexibility and its effect on the recognition between proteins and substrates associated with their important biological activity. The use of electrochemical-electron spin resonance (EC-ESR) assays and theoretical calculations at MP2/6-31G(d,p) and MP2/6-31++G(d,p)//MP2/6-31G(d,p) levels of several conformers of perezone [(2-(1,5-dimethyl-4-hexenyl)-3-hydroxy-5-methyl-1,4-benzoquinone] established that a weak pi-pi interaction controls not only the molecular conformation but also its diffusion coefficient and electrochemical properties. An analogous interaction can be suggested as the origin of similar properties of ubiquinone Q10. The use of nuclear magnetic resonance rendered, for the first time, direct evidence of the participation of different perezone conformers in solution and explained the cycloaddition process observed when the aforementioned quinone is heated to form pipitzols, sesquiterpenes with a cedrene skeleton. The fact that biological systems can modulate the redox potential of this type of quinones depending on the conformer recognized by an enzyme during a biological transformation is of great relevance.
authors.affiliation: Instituto de Química, Universidad Nacional Autónoma de México, Cd. Universitaria, Apdo. Postal 70213, 04510, México, D. F. México.
authors.forename: Guillermo
authors.initials: G
authors.lastname: Roura-Pérez
authors.forename: Beatriz
authors.initials: B
authors.lastname: Quiróz
authors.forename: Martha
authors.initials: M
authors.lastname: Aguilar-Martínez
authors.forename: Carlos
authors.initials: C
authors.lastname: Frontana
authors.forename: Alejandro
authors.initials: A
authors.lastname: Solano
authors.forename: Ignacio
authors.initials: I
authors.lastname: Gonzalez
authors.forename: José Antonio
authors.initials: JA
authors.lastname: Bautista-Martínez
authors.forename: Jesús
authors.initials: J
authors.lastname: Jiménez-Barbero
authors.forename: Gabriel
authors.initials: G
authors.lastname: Cuevas
mesh_terms: D001665:Binding Sites; D004578:Electron Spin Resonance Spectroscopy; D004583:Electrons; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D011809:Quinones / Q000737:chemistry*; D012717:Sesquiterpenes / Q000737:chemistry; D012996:Solutions
chemical_list: D011809:Quinones; D012717:Sesquiterpenes; D012996:Solutions; C053752:perezone