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Reaction equilibrium of the ω-transamination of (S)-Phenylethylamine: experiments and ePC-SAFT modeling

This work focuses on the thermodynamic equilibrium of the ω-transaminase-catalyzed reaction of (S)-phenylethylamine with cyclohexanone to acetophenone and cyclohexylamine in aqueous solution. For this purpose, the equilibrium concentrations of the reaction were experimentally investigated under vary...

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Main Authors: Voges, Matthias, Rohana, Abu, Gundersen, Maria T., Held, Christoph, Woodley, John M., Sadowski, Gabriele
Format: Article
Language:English
Published: American Chemical Society 2017
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TP Chemical technology
Online Access:http://umpir.ump.edu.my/id/eprint/29124/1/Reaction%20equilibrium%20of%20the%20%CF%89-transamination%20of%20%28S%29-Phenylethylamine.pdf
http://umpir.ump.edu.my/id/eprint/29124/
https://doi.org/10.1021/acs.oprd.7b00078
https://doi.org/10.1021/acs.oprd.7b00078
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spelling my.ump.umpir.291242022-11-07T06:13:16Z http://umpir.ump.edu.my/id/eprint/29124/ Reaction equilibrium of the ω-transamination of (S)-Phenylethylamine: experiments and ePC-SAFT modeling Voges, Matthias Rohana, Abu Gundersen, Maria T. Held, Christoph Woodley, John M. Sadowski, Gabriele TP Chemical technology This work focuses on the thermodynamic equilibrium of the ω-transaminase-catalyzed reaction of (S)-phenylethylamine with cyclohexanone to acetophenone and cyclohexylamine in aqueous solution. For this purpose, the equilibrium concentrations of the reaction were experimentally investigated under varying reaction conditions. It was observed that the temperature (30 and 37 °C), the pH (between pH 7 and pH 9), as well as the initial reactant concentrations (between 5 and 50 mmol·kg-1) influenced the equilibrium position of the reaction. The position of the reaction equilibrium was moderately shifted toward the product side by either decreasing temperature or decreasing pH. In contrast, the initial ratio of the reactants showed only a marginal influence on the equilibrium position. Further experiments showed that increasing the initial reactant concentrations significantly shifted the equilibrium position to the reactant side. In order to explain these effects, the activity coefficients of the reacting agents were calculated and the activity-based thermodynamic equilibrium constant Kth of the reaction was determined. For this purpose, the activity coefficients of the reacting agents were modeled at their respective experimental equilibrium concentrations using the equation of state electrolyte PC-SAFT (ePC-SAFT). The combination of the concentrations of the reacting agents at equilibrium and their respective activity coefficients provided the thermodynamically consistent equilibrium constant Kth. Unexpectedly, the experimental Km values deviated by a factor of up to four from the thermodynamic equilibrium constant Kth. The observed concentration dependency of the experimental Km values could be explained by the influence of concentration on activity coefficients. Further, these activity coefficients were found to be strongly temperature dependent, which is important for the determination of standard enthalpy of reactions, which in this work was found to be +7.7 ± 2.8 kJ·mol-1. Using the so-determined Kth and activity coefficients of the reacting agents (ePC-SAFT), the equilibrium concentrations of the reaction were predicted for varying initial reactant concentrations, which were found to be in good agreement with the experimental behavior. These results showed a non-negligible influence of the activity coefficients of the reacting agents on the equilibrium position and, thus, on the product yield. Experiments and ePC-SAFT predictions showed that the equilibrium position can only be described accurately by taking activity coefficients into account. American Chemical Society 2017-07-21 Article PeerReviewed pdf en http://umpir.ump.edu.my/id/eprint/29124/1/Reaction%20equilibrium%20of%20the%20%CF%89-transamination%20of%20%28S%29-Phenylethylamine.pdf Voges, Matthias and Rohana, Abu and Gundersen, Maria T. and Held, Christoph and Woodley, John M. and Sadowski, Gabriele (2017) Reaction equilibrium of the ω-transamination of (S)-Phenylethylamine: experiments and ePC-SAFT modeling. Organic Process Research and Development, 21 (7). pp. 976-986. ISSN 1083-6160 https://doi.org/10.1021/acs.oprd.7b00078 https://doi.org/10.1021/acs.oprd.7b00078
institution Universiti Malaysia Pahang
building UMP Library
collection Institutional Repository
continent Asia
country Malaysia
content_provider Universiti Malaysia Pahang
content_source UMP Institutional Repository
url_provider http://umpir.ump.edu.my/
language English
topic TP Chemical technology
spellingShingle TP Chemical technology
Voges, Matthias
Rohana, Abu
Gundersen, Maria T.
Held, Christoph
Woodley, John M.
Sadowski, Gabriele
Reaction equilibrium of the ω-transamination of (S)-Phenylethylamine: experiments and ePC-SAFT modeling
description This work focuses on the thermodynamic equilibrium of the ω-transaminase-catalyzed reaction of (S)-phenylethylamine with cyclohexanone to acetophenone and cyclohexylamine in aqueous solution. For this purpose, the equilibrium concentrations of the reaction were experimentally investigated under varying reaction conditions. It was observed that the temperature (30 and 37 °C), the pH (between pH 7 and pH 9), as well as the initial reactant concentrations (between 5 and 50 mmol·kg-1) influenced the equilibrium position of the reaction. The position of the reaction equilibrium was moderately shifted toward the product side by either decreasing temperature or decreasing pH. In contrast, the initial ratio of the reactants showed only a marginal influence on the equilibrium position. Further experiments showed that increasing the initial reactant concentrations significantly shifted the equilibrium position to the reactant side. In order to explain these effects, the activity coefficients of the reacting agents were calculated and the activity-based thermodynamic equilibrium constant Kth of the reaction was determined. For this purpose, the activity coefficients of the reacting agents were modeled at their respective experimental equilibrium concentrations using the equation of state electrolyte PC-SAFT (ePC-SAFT). The combination of the concentrations of the reacting agents at equilibrium and their respective activity coefficients provided the thermodynamically consistent equilibrium constant Kth. Unexpectedly, the experimental Km values deviated by a factor of up to four from the thermodynamic equilibrium constant Kth. The observed concentration dependency of the experimental Km values could be explained by the influence of concentration on activity coefficients. Further, these activity coefficients were found to be strongly temperature dependent, which is important for the determination of standard enthalpy of reactions, which in this work was found to be +7.7 ± 2.8 kJ·mol-1. Using the so-determined Kth and activity coefficients of the reacting agents (ePC-SAFT), the equilibrium concentrations of the reaction were predicted for varying initial reactant concentrations, which were found to be in good agreement with the experimental behavior. These results showed a non-negligible influence of the activity coefficients of the reacting agents on the equilibrium position and, thus, on the product yield. Experiments and ePC-SAFT predictions showed that the equilibrium position can only be described accurately by taking activity coefficients into account.
format Article
author Voges, Matthias
Rohana, Abu
Gundersen, Maria T.
Held, Christoph
Woodley, John M.
Sadowski, Gabriele
author_facet Voges, Matthias
Rohana, Abu
Gundersen, Maria T.
Held, Christoph
Woodley, John M.
Sadowski, Gabriele
author_sort Voges, Matthias
title Reaction equilibrium of the ω-transamination of (S)-Phenylethylamine: experiments and ePC-SAFT modeling
title_short Reaction equilibrium of the ω-transamination of (S)-Phenylethylamine: experiments and ePC-SAFT modeling
title_full Reaction equilibrium of the ω-transamination of (S)-Phenylethylamine: experiments and ePC-SAFT modeling
title_fullStr Reaction equilibrium of the ω-transamination of (S)-Phenylethylamine: experiments and ePC-SAFT modeling
title_full_unstemmed Reaction equilibrium of the ω-transamination of (S)-Phenylethylamine: experiments and ePC-SAFT modeling
title_sort reaction equilibrium of the ω-transamination of (s)-phenylethylamine: experiments and epc-saft modeling
publisher American Chemical Society
publishDate 2017
url http://umpir.ump.edu.my/id/eprint/29124/1/Reaction%20equilibrium%20of%20the%20%CF%89-transamination%20of%20%28S%29-Phenylethylamine.pdf
http://umpir.ump.edu.my/id/eprint/29124/
https://doi.org/10.1021/acs.oprd.7b00078
https://doi.org/10.1021/acs.oprd.7b00078
_version_ 1751536357567627264
score 13.211869

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