Proton‐Assisted Ethylene Hydration in Aqueous Solution

Erp, Titus S. van; Meijer, Evert Jan

doi:10.1002/anie.200353103

Cited by 28 publications

(27 citation statements)

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“…A similar approach was used to study the acid-catalyzed hydration of ethylene in aqueous solution. 31 The second part of the study focused on the catalytic mechanism occurring in the chiral environment provided by the LmrR protein. To embed the phen-Cu(II) catalyst into the LmrR dimer interface, protein−ligand dockings were performed throughout a covalent procedure as established in the GOLD 5.2 program, using the ChemScore scoring function.…”

Section: ■ Models and Methodsmentioning

confidence: 99%

Integrated Computational Study of the Cu-Catalyzed Hydration of Alkenes in Water Solvent and into the Context of an Artificial Metallohydratase

et al. 2019

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Despite the increasing efforts in the last few years, the identification of efficient catalysts able to perform the enantioselective addition of water to double bonds has not been achieved yet. Natural hydratases represent an interesting pool of biocatalysts to generate chiral alcohols, but modifying their substrate scope remains an issue. The use of artificial metalloenzymes (ArMs) appears as a promising solution in this field. In the last few years, Roelfes and co-workers have been designing a variety of DNA-and protein-based ArMs able to carry out the copper-mediated addition of water to conjugated alkenes with promising enantioselective levels. Still, from a mechanistic point of view, the copper-mediated hydration reaction remains unclear and a matter of debate. This lack of information greatly hampers further designs and optimizations of the LmrR-based copper hydratases in terms of substrates and/or enantioselective profiles. In this study, we aim to provide a better understanding of the copper-catalyzed hydration of alkenes occurring both in water solvent and into the context of the LmrR protein as designed by Roelfes and coworkers. For that purpose, we make use of an integrated computational protocol that combines quantum mechanics (QM) (including small and large cluster models as well as ab initio molecular dynamics (AIMD)) and force-field approaches (including protein−ligand docking and classical molecular dynamics (MD) simulation). This integrative study sheds light on the general doubts around the copper-catalyzed hydration mechanism and also paves the way toward more conscious designs of ArMs able to efficiently catalyze the enantioselective addition of water to double bonds.

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Section: ■ Models and Methodsmentioning

confidence: 99%

Integrated Computational Study of the Cu-Catalyzed Hydration of Alkenes in Water Solvent and into the Context of an Artificial Metallohydratase

et al. 2019

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“…͑44͒ and ͑48͒. 39, we found that electric field contributions due to nearby spontaneous formations of tetrahedral ordered water molecules can be crucial to give a last push over the potential energy barrier. Of course, one might object that the reactive flux methods for this 2D system improve dramatically if we would chose Ќ instead of x as RC.…”

Section: ͑61͒mentioning

confidence: 77%

“…In Ref. [39], we found that electric contributions due to nearby spontaneous formations of tetrahedral ordered water molecules can be crucial to give a last push over the potential energy barrier. To incorporate such an effect in a onedimensional RC would be an enormous task and can not be made without a priori insight in the mechanism.…”

Section: Tis: the θ > 0 Casementioning

confidence: 99%

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Efficiency analysis of reaction rate calculation methods using analytical models I: The two-dimensional sharp barrier

Erp¹

2006

The Journal of Chemical Physics

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We analyze the efficiency of different methods for the calculation of reaction rates in the case of a simple two-dimensional analytical benchmark system. Two classes of methods are considered: the first is based on the free energy calculation along a reaction coordinate and the calculation of the transmission coefficient, the second on the sampling of dynamical pathways. We give scaling rules for how this efficiency depends on barrier height and width, and we hand out simple optimization rules for the method-specific parameters. We show that the path sampling methods, using the transition interface sampling technique, become exceedingly more efficient than the others when the reaction coordinate is not the optimal one.

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“…In practice, it has been discovered that finding a good RC can be extremely difficult in high dimensional complex systems. Notable examples are chemical reactions in solution, where the reaction mechanism often depends on highly non-trivial solvent rearrangements [43]. Also, computer simulations of nucleation processes use very complicated order parameters to distinguish between particles belonging to the liquid and solid phase.…”

Section: Transition Path Samplingmentioning

confidence: 99%

Dynamical Rare Event Simulation Techniques for Equilibrium and Nonequilibrium Systems

Erp

2012

Kinetics and Thermodynamics of Multistep Nucleation and Self‐Assembly in Nanoscale Materials

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Proton‐Assisted Ethylene Hydration in Aqueous Solution

Cited by 28 publications

References 23 publications

Integrated Computational Study of the Cu-Catalyzed Hydration of Alkenes in Water Solvent and into the Context of an Artificial Metallohydratase

Integrated Computational Study of the Cu-Catalyzed Hydration of Alkenes in Water Solvent and into the Context of an Artificial Metallohydratase

Efficiency analysis of reaction rate calculation methods using analytical models I: The two-dimensional sharp barrier

Dynamical Rare Event Simulation Techniques for Equilibrium and Nonequilibrium Systems

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