Elucidating esterification reaction during deposition of cutin monomers from classical molecular dynamics simulations
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ORIGINAL PAPER
Elucidating esterification reaction during deposition of cutin monomers from classical molecular dynamics simulations Otto V. M. Bueno 1 & J. J. Benítez 2 & Miguel A. San-Miguel 1 Received: 2 May 2020 / Accepted: 14 September 2020 # Springer-Verlag GmbH Germany, part of Springer Nature 2020
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. Keywords Molecular dynamics . Esterification reaction . Self-assembly . Aleuritic acid . Palmitic acid
Introduction Fatty polyhydroxyacids (C16, C18) are the building monomers of ubiquitous biopolyesters such as cutin and suberin in higher plant tissues [1]. Both constitute the fourth most abundant plant biopolymer in nature after cellulose, hemicellulose, and lignin. In addition to the natural abundance, their extraordinary barrier capacity has attracted the interest for the This paper belongs to Topical Collection XX - Brazilian Symposium of Theoretical Chemistry (SBQT2019) Electronic supplementary material The online version of this article (https://doi.org/10.1007/s00894-020-04544-9) contains supplementary material, which is available to authorized users. * Miguel A. San-Miguel [email protected] 1
Department of Physical Chemistry, Institute of Chemistry, University of Campinas – UNICAMP, P.O. Box 6154, Campinas, SP 13083-970, Brazil
2
Instituto de Ciencias de Materiales de Sevilla, Centro Mixto CSIC-Universidad de Sevilla, Avda. Americo Vespuccio, 49, 41092 Sevilla, Spain
obtaining of synthetic mimetic polymers to replace hazardous and non-biodegradable petroleum-derived materials [2, 3]. Fatty polyhydroxyacids have been found to have the capability to self-assemble and self-esterify at an ambient condition to form nanometer-size particles named as cutinsomes [4]. Such nanoparticles have b
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