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Estimation of the solubility parameters of model plant surfaces and agrochemicals: a valuable tool for understanding plant surface interactions

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2012-11-14
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Fernández, Victoria
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Biomed Central Ltd
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Most aerial plant parts are covered with a hydrophobic lipid-rich cuticle, which is the interface between the plant organs and the surrounding environment. Plant surfaces may have a high degree of hydrophobicity because of the combined effects of surface chemistry and roughness. The physical and chemical complexity of the plant cuticle limits the development of models that explain its internal structure and interactions with surface-applied agrochemicals. In this article we introduce a thermodynamic method for estimating the solubilities of model plant surface constituents and relating them to the effects of agrochemicals. Results: Following the van Krevelen and Hoftyzer method, we calculated the solubility parameters of three model plant species and eight compounds that differ in hydrophobicity and polarity. In addition, intact tissues were examined by scanning electron microscopy and the surface free energy, polarity, solubility parameter and work of adhesion of each were calculated from contact angle measurements of three liquids with different polarities. By comparing the affinities between plant surface constituents and agrochemicals derived from (a) theoretical calculations and (b) contact angle measurements we were able to distinguish the physical effect of surface roughness from the effect of the chemical nature of the epicuticular waxes. A solubility parameter model for plant surfaces is proposed on the basis of an increasing gradient from the cuticular surface towards the underlying cell wall. Conclusions: The procedure enabled us to predict the interactions among agrochemicals, plant surfaces, and cuticular and cell wall components, and promises to be a useful tool for improving our understanding of biological surface interactions.
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© 2012 Khayet and Fernández; licensee BioMed Central Ltd. The authors wish to thank Dr. M. Steinbauer (La Trobe University, Victoria, Australia), Dr. M. A. Jenks (Western Regional USDA-ARS Biomass Research Center, USA) and E. P. Parsons (Purdue University, USA) for providing information on the composition of epicuticular waxes. We would like to thank the Electron Microscopy National Center (UCM; Madrid, Spain) for technical assistance with TEM. Victoria Fernández is supported by a "Ramón y Cajal" contract (MICINN, Spain), co-financed by the European Social Fund.
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1. Eichert T, Fernández V: Uptake and release of mineral elements by leaves and other aerial plant parts. In Marschner’s Mineral Nutrition of Higher Plants. Edited by Marschner P. San Diego: Academic Press; 2012:71–84. 2. Javelle M, Vernoud V, Rogowsky PM, Gwyneth CI: Epidermis: the formation and functions of a fundamental plant tissue. New Phytol 2011, 189:17–39. 3. Burton RA, Gidley MJ, Fincher GB: Heterogeneity in the chemistry, structure and function of plant cell walls. Nat Chem Biol 2010, 10:724–732. 4. Domínguez E, Heredia Guerrero JA, Heredia A: The biophysical design of plant cuticles: an overview. New Phytol 2011, 189:938–949. 5. Fernández V, Eichert T: Uptake of hydrophilic solutes through plant leaves: current state of knowledge and perspectives of foliar fertilization. Crit Rev Plant Sci 2009, 28:36–68. 6. Samuels AL, Kunst L, Jetter R: Sealing plant surfaces: cuticular wax formation by epidermal cells. Ann Rev Plant Biol 2008, 59:683–707. 7. Pollard M, Beisson F, Li Y, Ohlrogge JB: Building lipid barriers: biosynthesis of cutin and suberin. Trends Plant Sci 2008, 13:236–246. 8. Tyree MT, Scherbatskoy T, Tabor CA: Leaf cuticles behave as asymmetric membranes. Evidence from the measurement of diffusion potentials. Plant Physiol 1990, 92:103–109. 9. Jeffree CH: The fine structure of the plant cuticle. In Annual Plant Reviews, Volume 23. Biology of the Plant Cuticle. Volume 23rd edition. Edited by Riederer M, Müller C. Oxford: Blackwel; 2006:11–125. 10. Kosma DK, Bourdenx B, Bernard A, Parsons EP, Lü S, Joubès J, Jenks MA: The impact of water deficiency on leaf cuticle lipids of Arabidopsis. Plant Physiol 2009, 151:1918–1929. 11. Yeats TH, Buda GJ, Wang Z, Chehanovsky N, Moyle LC, Jetter R, Schaffer AA, Rose JKC: The fruit cuticles of wild tomato species exhibit architectural and chemical diversity, providing a new model for studying the evolution of cuticle function. Plant J 1012, 69:655–666. 12. Jeffree CE, Baker EA, Holloway PJ: Ultrastructure and recrystallization of plant epicuticular waxes. New Phytol 1975, 75:539–549. 13. Neinhuis C, Koch K, Barthlott W: Movement and regeneration of epicuticular wax through plant cuticles. Planta 2001, 213:427–434. 14. Koch K, Neinhuis C, Ensikat HJ, Barthlott W: Self assembly of epicuticular waxes on living plant surfaces imaged by atomic force microscopy (AFM). J Exp Bot 2004, 55:711–718. 15. Kolattukudy PE: Biopolyester membranes of plants: cutin and suberin. Science 1980, 208:990–1000. 16. Graça J, Lamosa P: Linear and branched poly(ω-hydroxyacid) esters in plant cutins. J Agric Food Chem 2010, 58(17):9666–9674. 17. Heredia Guerrero JA, Domínguez E, Luna M, Benítez JJ, Heredia A: Structural characterization of polyhydroxy fatty acid nanoparticles related to plant lipid biopolyesters. Chem Phys Lipids 2010, 163(3):329–333. 18. Villena JF, Domínguez E, Stewart D, Heredia A: Characterization and biosynthesis of non-degradable polymers in plant cuticles. Planta 1999, 208:181–187. 19. Johnson EJ, Chefetz B, Xing B: Spectroscopic characterization of aliphatic moieties in four plant cuticles. Comm Soil Sci Plant Anal 2007, 38:2461–2478. 20. Fernández V, Khayet M, Montero Prado P, Heredia Guerrero JA, Liakoloulos G, Karabourniotis G, Del Río V, Domínguez E, Tacchini I, Nerín C, Val J, Heredia A: New insights into the properties of pubescent surfaces: peach fruit as model. Plant Physiol 2011, 156(4):2098–2108. 21. Wagner P, Fürstner R, Barthlott W, Neinhuis C: Quantitative assessment to the structural basis of water repellency in natural and technical surfaces. J Exp Bot 2003, 54:1295–1303. 22. Ensikat HJ, Ditsche-Kuru P, Neinhuis C, Barthlott W: Superhydrophobicity in perfection: the outstanding properties of the lotus leaf. Beilstein J Nanotech 2011, 2:152–161. 23. Bhushan B, Jung YC: Natural and biomimetic artificial surfaces for superhydrophobicity, self- cleaning, low adhesion, and drag reduction. Progress Mater Sci 2010, 56:1 108. 24. Holloway PJ: The effects of superficial wax on leaf wettability. Ann Appl Biol 1969, 63:145–153. 25. Pandey S, Nagar PK: Pattern of leaf surface wetness in some important medicinal and aromatic plants of western Himalaya. Flora 2003, 198:349–357. 26. Aryal B, Neuner G: Leaf wettability decreases along an extreme altitudinal gradient. Oecol 2010, 162:1–9. 27. Burkhardt J: Hygroscopic particles on leaves: nutrients or desiccants? Ecol Monographs 2010, 80:369–399. 28. Burkhardt J, Basi S, Pariyar S, Hunsche M: Stomatal penetration by aqueous solutions – an update involving leaf surface particles. New Phytol, In press. 29. Kardel F, Wuyts K, Babanezhad M, Wuytack T, Adriaenssens S, Samson R: Tree leaf wettability as passive bio-indicator of urban habitat quality. Environ Exp Bot 2012, 75:277–285. 30. Neinhuis C, Barthlott W: Seasonal changes of leaf surface contamination in beech, oak, and ginkgo in relation to leaf micromorphology and wettability. New Phytol 1998, 138:91–98. 31. Kerstiens G: Cuticular water permeability and its physiological significance. J Exp Bot 1996, 47:1813–1832. 32. Riederer M, Friedmann A: Transport of lipophilic non-electrolytes across the cuticle. In Annual Plant Reviews, Volume 23. Biology of the Plant Cuticle. Edited by Riederer M, Müller C. Oxford: Blackwell; 2006:250–279. 33. Khayet M, Suk DE, Narbaitz RM, Santerre JP, Matsuura T: Study on surface modification by surface-modifying macromolecules and its applications in membrane separation processes. J Appl Polym Sci 2003, 89:2902–2916. 34. Khayet M, Vázquez Alvarez M, Khulbe KC, Matsuura T: Preferential surface segregation of homopolymer and copolymer blend films. Surface Sci 2007, 601:885–895. 35. Hansen CM: 50 Years with solubility parameters — past and future. Progress Organ Coatings 2004, 51:77–84. 36. Hancock BC, York P, Rowe RC: The use of solubility parameters in pharmaceutical dosage form design. Int J Pharma 1997, 148:1–21. 37. Gröning R, Braun FJ: Three dimensional solubility parameters and their use in characterising the permeation of drugs through the skin. Pharmazie 1996, 51:337–341. 38. Dias M, Hadgraft J, Lane ME: Influence of membrane–solvent–solute interactions on solute permeation in skin. Int J Pharma 2007, 340:65–70. 39. Bauer S, Schulte E, Thier HP: Composition of the surface waxes from bell pepper and eggplant. Eur Food Res Technol 2005, 220:5–10. 40. Kissinger M, Tuvia-Alkalai S, Shalom Y, Fallik E, Elkind Y, Jenks MA, Goodwin MS: Characterization of physiological and biochemical factors associated with postharvest water loss in ripe pepper fruit during storage. J Amer Soc Hort Sci 2005, 130:735–741. 41. Parsons EP, Popopvsky S, Lohrey GT, Lü S, Alkalai-Tuvia S, Perzelan Y, Paran I, Fallik E, Jenks MA: Fruit cuticle lipid composition and fruit postharvest water-loss in an advanced backcross generation of pepper (Capsicum sp.). Physiol Plant 2012, 146(1):15–25. 42. Li H, Madden JL, Potts BM: Variation in leaf waxes of the Tasmanian Eucalyptus species - I. Subgenus Symphyomyrtus. Biochem Systemat Ecol 1997, 25:631–657. 43. Wirthensohn MG, Sedgley M, Jones GP: Epicuticular wax of juvenile Eucalyptus leaves and headspace analysis of leaf volatiles. J Essential Oil Res 2000, 12:401–441. 44. Jones TH, Potts BM, Vaillancourt RE, Davies NW: Genetic resistance of Eucalyptus globulus to autumn gum moth defoliation and the role of cuticular waxes. Canad J Forest Res 2002, 32(11):1961–1969. 45. Rapley L, Allen GR, Potts BM: Susceptibility of Eucalyptus globulus to Mnesampela privata defoliation in relation to a specific foliar wax compound. Chemoecol 2004, 14(3–4):157–163. 46. Steinbauer MJ, Davies NW, Gaertner C, Derridj S: Epicuticular waxes and plant primary metabolites on the surfaces of juvenile Eucalyptus globulus and E. nitens (Myrtaceae) leaves. Aust J Bot 2009, 57:474–485. 47. Kolattukudy PE: Polyesters in higher plants. In Advances in biochemical engineering/ biotechnology. Edited by Scheper T. Berlin: Springer; 2001:4–49. 48. Kolattukudy PE: Cutin from plants. Biopolymers Online. Weinheim: Wiley-VCH Verlag GmbH; 2005. 49. O’Neill MA, York WS: The composition and structure of plant primary cell walls. In The Plant Cell Wall. Edited by Rose JKC. Oxford: Blackwell Publishing/CRC; 2005:1–54. 50. Khayet M, Chowdhury G, Matsuura T: Surface modification of polyvinylidene fluoride pervaporation membranes. AIChE J 2002, 48:2833–2843. 51. van Krevelen DW, te Nijenhuis K: Cohesive properties and solubility. In Properties of Polymers: Their Correlation with Chemical Structure; Their Numerical Estimation and Prediction from Additive Group Contributions. 4th edition. Edited by. Oxford: Elsevier; 2009:189–227. 52. van Krevelen DW, Hoftyzer PJ: Properties of polymers: their estimation and correlation with chemical structure. 2nd edition. Amsterdam: Elsevier; 1976. 53. Nosonovsky M, Bhushan B: Superhydrophobic surfaces and emerging applications: non-adhesion, energy, green engineering. Curr Opin Coll Interf Sci 2009, 14:270–280. 54. Wirthensohn MG, Sedgley M: Epicuticular wax structure and regeneration on developing juvenile Eucalyptus leaves. Aust J Bot 1996, 44(6):691–704. 55. Pariyar S, Eichert T, Goldbach HE, Hunsche M, Burkhardt J: The exclusion of ambient aerosols changes the water relations of sunflower (Helianthus annuus) and bean (Vicia faba) plants. Environ Exp Bot, In press. 56. Samaha MW, Naggar VF: Micellar properties of non-ionic surfactants in relation to their solubility parameters. Int J Pharma 1998, 42:1–9. 57. Schott H: Hydrophilic–lipophilic balance, solubility parameter, and oil–water partition coefficient as universal parameters of nonionic surfactants. J Pharma Sci 1995, 84:1215–1222. 58. Senichev VY, Tereshatov VV: General principles governing dissolution of materials in solvents. 4.1 Simple solvent characteristics. In Handbook of Solvents. Edited by Wypych G. Toronto: ChemTec; 2001:101–124. 59. Greenhalgh DJ, Williams AC, Timmins P, York P: Solubility parameters as predictors of miscibility in solid dispersions. J Pharma Sci 1999, 88:1182–1190. 60. Uhlig BA, Wissemeier AH: Reduction of non-ionic surfactant phytotoxicity by divalent cations. Crop Prot 2000, 19:13–19. 61. Scherbatskoy T, Tyree MT: Kinetics of exchange of ions between artificial precipitation and maple leaf surfaces. New Phytol 1990, 114:703–712. 62. Riederer M, Schönherr J: Development of plant cuticles fine structure and cutin composition of Clivia miniata Reg. leaves. Planta 1988, 174:127–138.
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