Effects of accelerators on mobility of 14C-2,4-dichlorophenoxy butyric acid in plant cuticles depends on type and concentration of accelerator.

Effects of diethyl suberate (DESU), diethyl sebacate (DES), dibutyl suberate (DBSU), dibutyl sebacate (DBS), and tributyl phosphate (TBP) on diffusion of 14C-2,4-dichlorophenoxy butyric acid (2,4-DB) across cuticular membranes (CM) was studied. Astomatous CM were isolated enzymatically from Stephanotis floribunda Brongn. leaves, and diffusion was measured at 20 degrees C. The alkyl-substituted dicarboxylic acids constitute a homologous series with carbon numbers increasing from C12 to C18. Molecular weights increased only moderately from 230.0 (DESU) to 314.5 (DBS), while partition coefficients varied over orders of magnitude from 92 (DESU), to 1213 (DES), to 15,988 (DBSU), to 210,762 (DBS). All the above compounds turned out to be accelerators as they increased 2,4-DB mobility by up to 40-fold with accelerator concentrations in the CM ranging from only 9.2 to 105 g kg(-1). Efficacy (2,4-DB mobility in the presence/mobility in the absence of accelerators) increased with increasing concentrations of accelerators in CM or in reconstituted cuticular waxes. Plotting efficacy vs accelerator concentration in the CM resulted in straight lines, and their slopes increased in the order DBS (0.14), DBSU (0.31), DES (0.51), and DESU (0.85). Hence, DESU was the most powerful accelerator in this series as it increased 2,4-DB mobility in the CM about 6 times more than DBSU. Waxes constitute the major barrier in plant cuticles, and plots of efficacy vs accelerator concentration in Stephanotis wax were also linear, but compared to CM slopes were steeper by factors of 3.20 (DBS), 2.97 (DBSU), 2.70 (DES), and 1.62 (DESU). TBP was similarly effective as DESU, but plots of efficacy vs concentration were not linear, and curves approached a plateau at 60-80 g kg(-1). These data are discussed with regard to suitability of these accelerators for formulating systemic pesticides.

Sorption in reconstituted waxes of homologous series of alcohol ethoxylates and n-alkyl esters and their effects on the mobility of 2,4-dichlorophenoxybutyric acid.

Equilibrium sorption of n-alkyl esters (dimethyl suberate, diethyl suberate, diethyl sebacate, dibutyl suberate and dibutyl sebacate) and monodisperse alcohol ethoxylates (diethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol and octaethylene glycol monododecyl ether) between the reconstituted cuticular waxes of Stephanotis floribunda Brongn (Madagascar jasmine) or Hordeum vulgare L (barley) leaves and an external aqueous receptor solution was determined. Logarithms of the wax/receptor partition coefficient (K(wax/rec)) of the n-alkyl esters increased linearly with the number of C-atoms. With alcohol ethoxylates, log K(wax/rec) decreased linearly with the number of ethylene oxide units. For both groups of compounds, K(wax/rec) increased with increasing lipophilicity. The values of K(wax/rec) in Stephanotis wax were between 5 and 16 times higher than in barley wax. It is argued that this difference was due to different chemical composition and crystallinity of the waxes. Mobility of [14C]2,4-dichlorophenoxybutyric acid (2,4-DB) in reconstituted Stephanotis and barley wax was increased by a factor of 2-8 by both n-alkyl esters and alcohol ethoxylates. Effects on the mobility of 2,4-DB were linearly related to the internal concentrations of n-alkyl esters and alcohol ethoxylates in reconstituted Stephanotis or barley wax. At the same internal concentrations the effect of n-alkyl esters on the mobility of 2,4-DB in wax exceeded that of alcohol ethoxylates by between 1 and 2 orders of magnitude. Results are discussed in relation to formulating systemic pesticides.

A new technique for measurement of water permeability of stomatous cuticular membranes isolated from Hedera helix leaves.

Transpiration of cuticular membranes isolated from the lower stomatous surface of Hedera helix (ivy) leaves was measured using a novel approach which allowed a distinction to be made between gas phase diffusion (through stomatal pores) and solid phase diffusion (transport through the polymer matrix membrane and cuticular waxes) of water molecules. This approach is based on the principle that the diffusivity of water vapour in the gas phase can be manipulated by using different gases (helium, nitrogen, or carbon dioxide) while diffusivity of water in the solid phase is not affected. This approach allowed the flow of water across stomatal pores ('stomatal transpiration') to be calculated separately from the flow across the cuticle (cuticular transpiration) on the stomatous leaf surface. As expected, water flux across the cuticle isolated from the astomatous leaf surface was not affected by the gas composition since there are no gas-filled pores. Resistance to flux of water through the solid cuticle on the stomatous leaf surface was about 11 times lower than cuticular resistance on the astomatous leaf surface, indicating pronounced differences in barrier properties between cuticles isolated from both leaf surfaces. In order to check whether this difference in resistance was due to different barrier properties of cuticular waxes on both leaf sides, mobility of 14C-labelled 2,4-dichlorophenoxy-butyric acid 14C-2,4-DB) in reconstituted cuticular wax isolated from both leaf surfaces was measured separately. However, mobility of 14C-2,4-DB in reconstituted wax isolated from the lower leaf surface was 2.6 times lower compared with the upper leaf side. The significantly higher permeability of the ivy cuticle on the lower stomatous leaf surface compared with the astomatous surface might result from lateral heterogeneity in permeability of the cuticle covering normal epidermal cells compared with the cuticle covering the stomatal cell surface.