Publicaciones 2011-2020

@article{RN394,
title = {Unraveling the Nature of the Catalytic Power of Fluoroacetate Dehalogenase},
author = { S. Miranda-Rojas and I. Fernandez and J. Kastner and A. Toro-Labbe and F. Mendizabal},
url = {/brokenurl#<Go to ISI>://WOS:000426844600026},
doi = {10.1002/cctc.201701517},
issn = {1867-3880},
year = {2018},
date = {2018-01-01},
journal = {Chemcatchem},
volume = {10},
number = {5},
pages = {1052-1063},
abstract = {Fluoroacetate dehalogenase is able to cleavage a carbon-fluoride bond, the strongest carbon-halogen bond in nature, in a process initiated by a S(N)2 reaction. The role of the enzyme machinery and particularly of the halogen pocket in the S(N)2 reaction is thoroughly explored by using state-of-the-art computational tools. A comparison between the non-catalyzed versus enzyme-catalyzed reaction, as well as with a mutant of the enzyme (Tyr219Phe), is presented. The energy barrier changes are rationalized by means of reaction force analysis and the activation strain model coupled with energy decomposition analysis. The catalysis is in part caused by the reduction of structural work from bringing the reactant species towards the proper reaction orientation, and the reduction of the electrostatic repulsion between the nucleophile and the substrate, which are both negatively charged. In addition, catalysis is also driven by an important reduction of the electronic reorganization processes during the reaction, where Tyr from the halogen pocket acts as a charge acceptor from the S(N)2 reaction axis therefore reducing the electronic steric repulsion between the reacting parts.},
keywords = {approach, bond, carbon-fluorine catalysis, chemical cluster decomposition density-functional displacement, dynamics, energy enzyme force, mechanism model, molecular-orbital qm/mm, transition-state},
pubstate = {published},
tppubtype = {article}
}

@article{RN105,
title = {Quantum Mechanical Continuum Solvation Models for Ionic Liquids},
author = { V.S. Bernales and A.V. Marenich and R. Contreras and C.J. Cramer and D.G. Truhlar},
url = {/brokenurl#<Go to ISI>://WOS:000306989800043},
doi = {10.1021/jp304365v},
issn = {1520-6106},
year = {2012},
date = {2012-01-01},
journal = {Journal of Physical Chemistry B},
volume = {116},
number = {30},
pages = {9122-9129},
abstract = {The quantum mechanical SMD continuum universal solvation model can be applied to predict the free energy of solvation of any solute in any solvent following specification of various macroscopic solvent parameters. For three ionic liquids where these descriptors are readily available, the SMD solvation model exhibits a mean unsigned error of 0.48 kcal/mol for 93 solvation free energies of neutral solutes and a mean unsigned error of 1.10 kcal/mol for 148 water-to-IL transfer free energies. Because the necessary solvent parameters are not always available for a given ionic liquid, we determine average values for a set of ionic liquids over which measurements have been made in order to define a generic ionic liquid solvation model, SMD-GIL. Considering 11 different ionic liquids, the SMD-GIL solvation model exhibits a mean unsigned error of 0.43 kcal/mol for 344 solvation free energies of neutral solutes and a mean unsigned error of 0.61 kcal/mol for 431 water-to-IL transfer free energies. As these errors are similar in magnitude to those typically observed when applying continuum solvation models to ordinary liquids, we conclude that the SMD universal solvation model may be applied to ionic liquids as well as ordinary liquids.},
keywords = {ab-initio, approach, carbon-dioxide, density dielectric-constant, free-energies, functionals, gas-phase green kinetics, molecular-dynamics simulations, solvents, static thermochemical universal},
pubstate = {published},
tppubtype = {article}
}