TY - JOUR
T1 - Quantification of Structure-Property Relationships for Plant Polyesters Reveals Suberin and Cutin Idiosyncrasies
AU - Bento, Artur
AU - Moreira, Carlos J.S.
AU - Correia, Vanessa G.
AU - Escórcio, Rita
AU - Rodrigues, Rúben
AU - Tomé, Ana S.
AU - Geneix, Nathalie
AU - Petit, Johann
AU - Bakan, Bénédicte
AU - Rothan, Christophe
AU - Mykhaylyk, Oleksandr O.
AU - Silva Pereira, Cristina
N1 - Funding Information:
C.J.S.M. and V.G.C. contributed equally. C.S.P and O.O.M. contributed to conceptualization. C.S.P. and O.O.M. were responsible for funding acquisition. Project administration and supervision was done by C.S.P. C.S.P., O.O.M., B.B., and C.R. contributed to resources. All authors contributed to investigation and methodology. Formal analysis was conducted by A.B., C.J.S.M., V.G.C., and O.O.M. Validation, visualization, and writing─original draft were performed by A.B., C.J.S.M., and V.G.C. All authors contributed to writing─review and editing.
Publisher Copyright:
© 2021 The Authors. Published by American Chemical Society.
PY - 2021/11/29
Y1 - 2021/11/29
N2 - 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.
AB - 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.
KW - biopolymers
KW - crystallinity
KW - ionic liquids
KW - plant industrial residues
KW - quantitative NMR
KW - thermal resistance
UR - http://www.scopus.com/inward/record.url?scp=85120003319&partnerID=8YFLogxK
U2 - 10.1021/acssuschemeng.1c04733
DO - 10.1021/acssuschemeng.1c04733
M3 - Article
AN - SCOPUS:85120003319
SN - 2168-0485
VL - 9
SP - 15780
EP - 15792
JO - ACS Sustainable Chemistry & Engineering
JF - ACS Sustainable Chemistry & Engineering
IS - 47
ER -