ABSTRACT
The aim was to quantify the softening effect that two surfactants (C10EO7 and C8G1.6) have on a plant leaf cuticle model wax. Effects on the thermotropic phase behavior and fluidity of the wax (C22H45OH/C32H66/H2O) were determined. The model wax is crystalline at ambient conditions, yet it is clearly softened by the surfactants. Both surfactants decreased the transition temperatures in the wax and the Gâ³/G' ratio of the wax film increased in irreversible steps following surfactant exposure. C10EO7 has a stronger fluidizing effect than C8G1.6 due to stronger interaction with the hydrophobic waxes. Intracuticular waxes (IW) comprise both crystalline and amorphous domains and it has previously been proposed that the fluidizing effects of surfactants are due to interactions with the amorphous parts. New data suggests that this may be a simplification. Surfactants may also absorb in crevices between crystalline domains. This causes an irreversible effect and a softer cuticle wax.
Subject(s)
Calorimetry, Differential Scanning/methods , Plants/chemistry , Quartz , Surface-Active Agents/chemistry , Waxes , Models, Biological , RheologyABSTRACT
The main objective of this study was to investigate the mechanism of molecular transport across the cuticle of Clivia leaves. In vitro diffusion methodology was used to investigate the transport of a systemic fungicide, tebuconazole, over a model silicone membrane, enzymatically isolated cuticle membranes, and dermatomed leaves. It was shown that dermatomed leaves may replace enzymatically isolated cuticles. Furthermore, the effects of two surfactants, C(10)EO(7) and C(8)G(1.6), on the fungicide transport were investigated. Tebuconazole cuticle permeation was described using Fick's first law of diffusion, expressed by the thermodynamic activity of the solute in the membrane. A new method for calculation of diffusion coefficients in the membrane is proposed. To access the thermodynamic activity of the fungicide in the membranes, sorption isotherms of tebuconazole in the membrane materials studied were recorded. The thermodynamic activity of the fungicide in aqueous solutions was calculated from solubility data. For that purpose, the effect of surfactants on tebuconazole solubility was studied. The results show that addition of surfactants allows for higher concentrations of tebuconazole available for penetration. Nonetheless, at a fixed fungicide thermodynamic activity, all formulations produced the same flux over the silicone membrane independently on the fungicide concentration. This shows that the driving force across non-responding membranes is the gradient of thermodynamic activity, rather than the gradient of the fungicide concentration. In case of leaves, surfactants induced the same quantitative increase in both flux and diffusion coefficient of solute in the cuticle, while the cuticle-water partition coefficient was unaffected.
