The penetration of the wax barrier
of plant cuticles is the rate-limiting
step for the uptake of surface applied pesticides. Optimizing the
uptake rates of active ingredients across this barrier is a significant
objective of the rational design of pesticide formulations. We used
an ATR-FTIR-based method for determining the diffusion coefficients
derived from Fickian diffusion kinetics in paraffin wax of model diffusants
differing in chemical structure, lipophilicity, and size at different
temperatures. At 25 °C, the diffusion coefficients of 4-cyanophenol
and heptyl parabene were 1.48 × 10–15 and 1.73
× 10–15 m2 s–1, respectively, and increased from 25 to 40 °C yielding activation
energies of 54 kJ mol–1 and 71 kJ mol–1, respectively. In contrast, much higher diffusion coefficients were
obtained for the accelerating adjuvants methyl oleate (1.49 ×
10–13 m2 s–1) and C12E2
(4.52 × 10–14 m2 s–1), exhibiting entirely Fickian diffusion kinetics. The diffusion
coefficients in wax are 3–5 orders of magnitude lower than
diffusion coefficients in water predicted for these molecules, which
illustrates the massive barrier the cuticle forms against the uptake
of solutes. The current work demonstrates ATR-FTIR’s suitability
as a new approach to optimizing pesticide formulations by quantitatively
investigating active ingredient and adjuvant mobility in thin wax
films.
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