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. 2020 Oct 8;5(41):26795-26806.
doi: 10.1021/acsomega.0c02405. eCollection 2020 Oct 20.

Kinetic Modeling of a Consecutive Enzyme-Catalyzed Enantioselective Reaction in Supercritical Media

Michael Freitas Gustavo  1 , Edit Székely  1 , János Tóth  2   3
Affiliations

Kinetic Modeling of a Consecutive Enzyme-Catalyzed Enantioselective Reaction in Supercritical Media

Michael Freitas Gustavo et al. ACS Omega. .

Abstract

Based on experimental data of both batch and continuous enzyme-catalyzed kinetic resolutions of (±)-trans-1,2-cyclohexanediol in supercritical carbon dioxide, kinetic models of increasing complexity were developed to explore the strengths and drawbacks of various modeling approaches. The simplest, first-order model proved to be a good fit for the batch experimental data in regions of high reagent concentrations but failed elsewhere. A more complex system that closely follows the true mechanism was able to fit the full range of experimental data, find constant reaction rate coefficients, and was successfully used to predict the results of the same reaction run continuously in a packed bed reactor. Care must be taken when working with such models, however, to avoid problems of overfitting; a more complex model is not always more accurate. This work may serve as an example for more rigorous reaction modeling and reactor design in the future.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Reaction Scheme of the Ping–Pong Bi–Bi Acylation of trans-1,2-Cyclohexanediol
Scheme 2
Scheme 2. Model A for the Acylation of trans-1,2-Cyclohexanediol
Scheme 3
Scheme 3. Model B for the Acylation of trans-1,2-Cyclohexanediol
Scheme 4
Scheme 4. Model C for the Acylation of trans-1,2-Cyclohexanediol
Scheme 5
Scheme 5. Model D for the Acylation of trans-1,2-Cyclohexanediol
Figure 1
Figure 1
Calculated kinetic rate coefficients as a function of VA for the four models based on batch reaction data.
Figure 2
Figure 2
AICc values for each model fit at different VA molar ratios.
Figure 3
Figure 3
Batch experimental concentration versus time values for the cyclohexane species at a low vinyl acetate molar ratio (2 MR VA) with four model curves.
Figure 4
Figure 4
Batch experimental concentration versus time values for the cyclohexane species at 10 MR VA with four model curves.
Figure 5
Figure 5
Experimental and modeled reaction yields as a function of residence time for continuous packed bed operation at a steady state.
Figure 6
Figure 6
Experimental and modeled turnover frequencies as a function of residence time for continuous packed bed operation at a steady state.
Figure 7
Figure 7
Experimental and modeled productivities as a function of residence time for continuous packed bed operation at a steady state.
Scheme 6
Scheme 6. Reaction Scheme of CAL-B-Catalyzed Consecutive Acylation of (±)-1 with Vinyl Acetate as the Acylation Agent
See this image and copyright information in PMC

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