Observatorio de I+D+i UPM

Memorias de investigación
Research Publications in journals:
Structures and thermodynamics of biphenyl dihydrodiol stereoisomers and their metabolites in the enzymatic degradation of arene xenobiotics
Year:2009
Research Areas
  • Molecular biology
Information
Abstract
Abstract A key step in the metabolic degradation of biphenyl xenobiotics is catechol formation upon dehydrogenation of cis- and trans-dihydrodiols in prokaryotic and eukaryotic pathways, respectively. Structure and thermodynamics of stereoisomers of cis-, trans-2,3-biphenyl-dihydrodiols (I) and their dehydrogenation products (hydroxyketones, II), as well as final catechol (2,3-biphenyldiol, III) are studied by means of ab initio MP2/6-311++G(2df,2p)//MP2/6-311G(d,p) calculations. Formation of stereoisomers I and II is exothermic and endergonic, whereas III is enthalpically and entropically driven. Dehydrogenations are endothermic (¿H ~ 1.5¿4 kcal mol¿1) and exergonic (¿G ~ ¿5 to ¿7.5 kcal mol¿1) without noticeable differences between cis and trans pathways, although the same keto stereoisomer II-(2S) is found to be the more favored product from both cis- and trans-I. The final II ¿ III tautomerization is thermodynamically enhanced (¿H ~ ¿27, ¿G ~ ¿28 kcal mol¿1) but the process is shown to have a large activation energy if it had to occur via unimolecular path. Although this tautomerization is generally assumed to be a nonenzymatic process as it involves rearomatization of an oxygenated ring, proton transfer with an anionic intermediate might be a more probable process. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009
International
Si
JCR
Si
Title
JOURNAL OF COMPUTATIONAL CHEMISTRY
ISBN
0192-8651
Impact factor JCR
3,39
Impact info
Volume
Journal number
0
From page
2420
To page
2432
Month
ENERO
Ranking
Participants
  • Participante: Luis F. Pacios
  • Autor: Victor Manuel Campos Del Pozo (UPM)
  • Autor: Luis Gomez Fernandez (UPM)
  • Autor: Irene María Merino Sierra (UPM)
Research Group, Departaments and Institutes related
  • Creador: Centro o Instituto I+D+i: Centro de Biotecnología y Genómica de Plantas, CBGP
  • Departamento: Biotecnología
S2i 2020 Observatorio de investigación @ UPM con la colaboración del Consejo Social UPM
Cofinanciación del MINECO en el marco del Programa INNCIDE 2011 (OTR-2011-0236)
Cofinanciación del MINECO en el marco del Programa INNPACTO (IPT-020000-2010-22)