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Elucidating esterification reaction during deposition of cutin monomers from classical molecular dynamics simulations

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Abstract

The structural behavior of some cutin monomers, when deposited on mica support, was extensively investigated by our research group. However, other events, such as esterification reaction (ER), are still a way to explore. In this paper, we explore possible ER that could occur when these monomers adsorb on support. Although classical molecular dynamics simulations are not able to capture reactive effects, here, we show that they become valuable strategies to analyze the initial structural configurations to predict the most favorable reaction routes. Thus, when depositing aleuritic acid (ALE), it is observed that the loss of capacity to form self-assembled (SA) systems favors different routes to occur ER. In pure ALE bilayers systems, an ER is given exclusively through the –COOH and primary –OH groups. In pure ALE monolayers systems, the ER does not happen when the system is self-assembled. However, for disorganized systems, it is able to occur by two possible routes: –COOH and primary –OH (route 1) and –COOH and secondary –OH (route 2). When palmitic acid (PAL) is added in small quantities, ALE SAMs can now form an ER. In this case, ER occurs mostly through the –COOH and secondary –OH groups. However, when the presence of PAL is dominant, ER can occur with either of both possibilities, that is, routes 1 and 2.

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The data that supports the findings of this study are available within the article [and its supplementary material].

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Acknowledgments

This work used computational resources from the “Centro Nacional de Processamento de Alto Desempenho em São Paulo” (CENAPAD-SP), “Centro de Computação John David Rogers” (CCJDR-UNICAMP), and the CENAPAD-RJ (SDumont).

Funding

This work was funded in part by the Fundação de Amparo à Pesquisa do Estado de São Paulo - FAPESP (2013/07296-2; 2016/23891-6) and the National Council for the Improvement of Higher Education (CAPES).

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Authors and Affiliations

  1. Department of Physical Chemistry, Institute of Chemistry, University of Campinas – UNICAMP, P.O. Box 6154, Campinas, SP, 13083-970, Brazil

    Otto V. M. Bueno & Miguel A. San-Miguel

  2. Instituto de Ciencias de Materiales de Sevilla, Centro Mixto CSIC-Universidad de Sevilla, Avda. Americo Vespuccio, 49, 41092, Sevilla, Spain

    J. J. Benítez

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  1. Otto V. M. Bueno
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  2. J. J. Benítez
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  3. Miguel A. San-Miguel
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All authors contributed equally to this work.

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Correspondence to Miguel A. San-Miguel.

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This paper belongs to Topical Collection XX - Brazilian Symposium of Theoretical Chemistry (SBQT2019)

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Bueno, O.V.M., Benítez, J.J. & San-Miguel, M.A. Elucidating esterification reaction during deposition of cutin monomers from classical molecular dynamics simulations. J Mol Model 26, 280 (2020). https://doi.org/10.1007/s00894-020-04544-9

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