1. Quantification of structure-property relationships for plant polyesters reveals suberin and cutin idiosyncrasies
- Author
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Rúben Rodrigues, Ana S. Tomé, Nathalie Geneix, Cristina Silva Pereira, Artur Bento, Johann Petit, Bénédicte Bakan, Carlos J. S. Moreira, Rita Escórcio, Vanessa G. Correia, Christophe Rothan, Oleksandr O. Mykhaylyk, Instituto de Tecnologia Química e Biológica António Xavier (ITQB), Universidade Nova de Lisboa = NOVA University Lisbon (NOVA), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Biologie du fruit et pathologie (BFP), Université de Bordeaux (UB)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), University of Sheffield [Sheffield], European Project: 647928,H2020,ERC-2014-CoG,MIMESIS(2015), European Project: 713475,FLIPT, and The authors acknowledge funding from the European Research Council through grant ERC 2014-CoG-647928, from the European Union's Horizon 2020 research and innovation program within the project 713475-FLIPT-H2020-FETOPEN-2014-2015, and from Fundacao para a Ciencia e Tecnologia (FCT) by Project MOSTMICRO ITQB with refs UIDB/04612/2020 and UIDP/04612/2020. The NMR data were acquired at CERMAX, ITQB NOVA, Oeiras, Portugal, with equipment funded by FCT. C.J.S.M. is grateful to Aralab, Portugal, for the PhD contract 06/PlantsLife/2017. O.O.M. thanks EPSRC for a capital equipment grant to purchase the Xenocs/Excillum SAXS/WAXS laboratory beamline (EP/M028437/1). The authors are thankful to Pedro Lamosa and Maria C. Leita~o (ITQB NOVA) for support with the NMR and chromatographic analyses, respectively, and to James Yates (ITQB NOVA) for proofreading the manuscript.
- Subjects
0106 biological sciences ,General Chemical Engineering ,plant industrial residues ,[SDV]Life Sciences [q-bio] ,biopolymers ,Cutin ,01 natural sciences ,ionic liquids ,03 medical and health sciences ,Suberin ,Environmental Chemistry ,[SDV.BV]Life Sciences [q-bio]/Vegetal Biology ,crystallinity ,030304 developmental biology ,0303 health sciences ,Polymer science ,Renewable Energy, Sustainability and the Environment ,Chemistry ,thermal resistance ,Structure property ,food and beverages ,General Chemistry ,Polyester ,quantitative NMR ,Research Article ,010606 plant biology & botany - Abstract
Polyesters, as they exist in planta, are promising materials with which to begin the development of “green” replacements. Cutin and suberin, polyesters found ubiquitously in plants, are prime candidates. Samples enriched for plant polyesters, and in which their native backbones were largely preserved, were studied to identify “natural” structural features; features that influence critical physical properties. Quantitative nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), and X-ray scattering methods were used to quantify structure–property relationships in these polymeric materials. The degree of esterification, namely, the presence of acylglycerol linkages in suberin and of secondary esters in cutin, and the existence of mid-chain epoxide groups defining the packing of the aliphatic chains were observed. This packing determines polymer crystallinity, the resulting crystal structure, and the melting temperature. To evaluate the strength of this rule, tomato cutin from the same genotype, studying wild-type plants and two well-characterized mutants, was analyzed. The results show that cutin’s material properties are influenced by the amount of unbound aliphatic hydroxyl groups and by the length of the aliphatic chain. Collectively, the acquired data can be used as a tool to guide the selection of plant polyesters with precise structural features, and hence physicochemical properties., A detailed insight into plant polyesters identifies correlations of structural features with physical properties that are translated into five essential rules for the development of novel green materials.
- Published
- 2021
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