Abstract
Biomimetics of materials is based on adopting and reproducing a model in nature with a well-defined functionality optimized through evolution. An example is barrier polymers that protect living tissues from the environment. The protecting layer of fruits, leaves, and non-lignified stems is the plant cuticle. The cuticle is a complex system in which the cutin is the main component. Cutin is a biopolyester made of polyhydroxylated carboxylic acids of 16 and 18 carbon atoms. The biosynthesis of cutin in plants is not well understood yet, but a direct chemical route involving the self-assembly of either molecules or molecular aggregates has been proposed. In this work, we present a combined study using experimental and simulation techniques on self-assembled layers of monomers selectively functionalized with hydroxyl groups. Our results demonstrate that the number and position of the hydroxyl groups are critical for the interaction between single molecules and the further rearrangement. Also, the presence of lateral hydroxyl groups reinforces lateral interactions and favors the bi-dimensional growth (2D), while terminal hydroxyl groups facilitate the formation of a second layer caused by head–tail interactions. The balance of 2D/3D growth is fundamental for the plant to create a protecting layer both large enough in 2D and thick enough in 3D.
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References
Arrieta-Baez D, Cruz-Carrillo M, Gómez-Patiño MB, Zepeda-Vallejo LG (2011) Derivatives of 10,16-dihydroxyhexadecanoic acid isolated from tomato (Solanum lycopersicum) as potential material for aliphatic polyesters. Molecules 16:4923–4936. doi:10.3390/molecules16064923
Domínguez E, Heredia-Guerrero JA, Benítez JJ, Heredia A (2010) Self-assembly of supramolecular lipid nanoparticles in the formation of plant biopolyester cutin. Mol BioSyst 6:948–950. doi:10.1039/B927186D
Smith W, Yong CW, Rodger PM (2002) DL_POLY: application to molecular simulation. Mol Simul 28:385–471. doi:10.1080/08927020290018769
Available at www.ccp5.ac.uk/DL_POLY
Nose S (1984) A unified formulation of the constant temperature molecular dynamics methods. J Chem Phys 81:511–519
Nose S (2002) A molecular dynamics method for simulations in the canonical ensemble. Mol Phys 100:191–198. doi:10.1080/00268970110089108
Hautman J, Klein ML (1992) An Ewald summation method for planar surfaces and interfaces. Mol Phys 75:379–395. doi:10.1080/00268979200100301
Heredia-Guerrero JA, San-Miguel MA, Sansom MSP, Heredia A, Benitez JJ (2009) Chemical reactions in 2D: self-assembly and self-esterification of 9(10),16-dihydroxypalmitic acid on mica surface. Langmuir 25:6869–6874. doi:10.1021/la9001412
Heredia-Guerrero JA, San-Miguel MA, Sansom MSP, Heredia A, Benitez JJ (2010) Aleuritic (9,10,16-trihydroxypalmitic) acid self-assembly on mica. Phys Chem Chem Phys 12:10423–10428. doi:10.1039/c0cp00163e
Heredia-Guerrero JA, San-Miguel MA, Luna M, Domínguez E, Heredia A, Benítez JJ (2011) Structure and support induced structure disruption of soft nanoparticles obtained from hydroxylated fatty acids. Soft Matter 7:4357–4363. doi:10.1039/c0sm01545h
San-Miguel MA, Rodger PM (2001) Simulation of deposition of wax to iron oxide surfaces. Mol Simul 26:193–216. doi:10.1080/08927020108028293
Jorgensen WL (1986) Optimized intermolecular potential functions for liquid alcohols. J Phys Chem 90:1276–1284
Briggs JM, Nguyen TB, Jorgensen WL (1991) Monte Carlo simulations of liquid acetic acid and methyl acetate with the OPLS potential functions. J Phys Chem 95:3315–3322
Hautman J, Klein ML (1989) Simulation of a monolayer of alkyl thiol chains. J Chem Phys 91:4994–5001
Fartaria RPS, Freitas FFM, Silva Fernandes FMS (2005) A study of 1-decanethiol self-assembly on gold electrodes by computer simulation. J Electroanal Chem 574:321–331. doi:10.1016/j.jelechem.2004.08.015
Benítez JJ, Heredia-Guerrero JA, Heredia A (2007) Self-assembly of carboxylic acids and hydroxyl derivatives on mica. A qualitative AFM study. J Phys Chem C 111:9465–9470. doi:10.1021/jp070563y
Cyr DM, Venkataraman B, Flynn GW (1996) STM investigations of organic molecules physisorbed at the liquid–solid interface. Chem Mater 8:1600–1615
Oian P, Nanjo H, Yokoyama T, Suzuki TM (1999) STM observation of 12-hydroxyoctadecanoic acid and its 4,4′-bipyridinium salt self-assembled on a graphite surface. Chem Commun 13:1197–1198
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Funding for this work was provided by the Spanish Ministerio de Economía y Competitividad under project CTQ2011-24299 and by Junta de Andalucía grant TEP-7418 under the Motriz Program.
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San-Miguel, M.A., Oviedo, J., Heredia-Guerrero, J.A. et al. Biomimetic polymers of plant cutin: an approach from molecular modeling. J Mol Model 20, 2329 (2014). https://doi.org/10.1007/s00894-014-2329-y
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DOI: https://doi.org/10.1007/s00894-014-2329-y