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Quantifying the Stability of the Hydronium Ion in Organic Solvents With Molecular Dynamics Simulations.
Front Chem. 2019; 7:439.FC

Abstract

The solution-phase stability of the hydronium ion catalyst significantly affects the rates of acid-catalyzed reactions, which are ubiquitously utilized to convert biomass to valuable chemicals. In this work, classical molecular dynamics simulations were performed to quantify the stability of hydronium and chloride ions by measuring their solvation free energies in water, 1,4-dioxane (DIOX), tetrahydrofuran (THF), γ-valerolactone (GVL), N-methyl-2-pyrrolidone (NMP), acetone (ACE), and dimethyl sulfoxide (DMSO). By measuring the free energy for transferring a hydronium ion from pure water to pure organic solvent, we found that the hydronium ion is destabilized in DIOX, THF, and GVL and stabilized in NMP, ACE, and DMSO relative to water. The distinction between these organic solvents can be used to predict the preference of the hydronium ion for specific regions in aqueous mixtures of organic solvents. We then incorporated the stability of the hydronium ion into a correlative model for the acid-catalyzed conversion of 1,2-propanediol to propanal. The revised model is able to predict experimental reaction rates across solvent systems with different organic solvents. These results demonstrate the ability of classical molecular dynamics simulations to screen solvent systems for improved acid-catalyzed reaction performance.

Authors+Show Affiliations

Department of Chemical and Biological Engineering, University of Wisconsin - Madison, Madison, WI, United States.Department of Chemical and Biological Engineering, University of Wisconsin - Madison, Madison, WI, United States.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31275924

Citation

Chew, Alex K., and Reid C. Van Lehn. "Quantifying the Stability of the Hydronium Ion in Organic Solvents With Molecular Dynamics Simulations." Frontiers in Chemistry, vol. 7, 2019, p. 439.
Chew AK, Van Lehn RC. Quantifying the Stability of the Hydronium Ion in Organic Solvents With Molecular Dynamics Simulations. Front Chem. 2019;7:439.
Chew, A. K., & Van Lehn, R. C. (2019). Quantifying the Stability of the Hydronium Ion in Organic Solvents With Molecular Dynamics Simulations. Frontiers in Chemistry, 7, 439. https://doi.org/10.3389/fchem.2019.00439
Chew AK, Van Lehn RC. Quantifying the Stability of the Hydronium Ion in Organic Solvents With Molecular Dynamics Simulations. Front Chem. 2019;7:439. PubMed PMID: 31275924.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Quantifying the Stability of the Hydronium Ion in Organic Solvents With Molecular Dynamics Simulations. AU - Chew,Alex K, AU - Van Lehn,Reid C, Y1 - 2019/06/19/ PY - 2019/02/13/received PY - 2019/05/28/accepted PY - 2019/7/6/entrez PY - 2019/7/6/pubmed PY - 2019/7/6/medline KW - acid-catalyzed reactions KW - biomass conversion KW - classical molecular dynamics simulation KW - hydronium ion KW - solvation free energy KW - solvent effects SP - 439 EP - 439 JF - Frontiers in chemistry JO - Front Chem VL - 7 N2 - The solution-phase stability of the hydronium ion catalyst significantly affects the rates of acid-catalyzed reactions, which are ubiquitously utilized to convert biomass to valuable chemicals. In this work, classical molecular dynamics simulations were performed to quantify the stability of hydronium and chloride ions by measuring their solvation free energies in water, 1,4-dioxane (DIOX), tetrahydrofuran (THF), γ-valerolactone (GVL), N-methyl-2-pyrrolidone (NMP), acetone (ACE), and dimethyl sulfoxide (DMSO). By measuring the free energy for transferring a hydronium ion from pure water to pure organic solvent, we found that the hydronium ion is destabilized in DIOX, THF, and GVL and stabilized in NMP, ACE, and DMSO relative to water. The distinction between these organic solvents can be used to predict the preference of the hydronium ion for specific regions in aqueous mixtures of organic solvents. We then incorporated the stability of the hydronium ion into a correlative model for the acid-catalyzed conversion of 1,2-propanediol to propanal. The revised model is able to predict experimental reaction rates across solvent systems with different organic solvents. These results demonstrate the ability of classical molecular dynamics simulations to screen solvent systems for improved acid-catalyzed reaction performance. SN - 2296-2646 UR - https://www.unboundmedicine.com/medline/citation/31275924/Quantifying_the_Stability_of_the_Hydronium_Ion_in_Organic_Solvents_With_Molecular_Dynamics_Simulations L2 - https://doi.org/10.3389/fchem.2019.00439 DB - PRIME DP - Unbound Medicine ER -
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