Influence of some nonionic surfactants on water sorption by isolated tomato fruit cuticles in relation to cuticular penetration of glyphosate

The effects of several nonionic surfactants on [¹⁴C]glyphosate mono(isopropylammonium) diffusion across isolated tomato fruit cuticles (Lycopersicon esculentum Mill.) were compared under controlled atmospheric conditions (25°C; 65% R.H.) using a model system consisting of 1-μl droplets applied to isolated cuticles on agar blocks. Rates of diffusion for glyphosate (10 g acid equivalent litre^?1 in the applied solution) and overall amounts recovered in underlying agar blocks were influenced by the ethylene oxide (EO) chain length for a homologous nonylphenol surfactant series (10 g litre^?1). Glyphosate uptake increased with EO content, reaching an optimum at a mean of 17 EO, then decreasing below control values for surfactants with 40 EO. There was a strong influence of the hydrophobe on glyphosate penetration for different surfactants with similar mean EO content (10 EO). The primary aliphatic amine enhanced penetration the most, followed by the nonylphenol while the aliphatic alcohol showed no improvement on glyphosate transfer across cuticles. Water soprtion was greatly enhanced by a primary aliphatic amine (10 EO) and by a nonylphenol (17 EO). The aliphatic alcohol (10 EO) and a shorter-chained nonylphenol (4 EO) did not significantly enhance water sorption. Comparison of water sorption with glyphosate diffusion across cuticles suggests a strong relationship between the two. Change in solution pH over a limited range had no significant effect. Promotion of cuticular hydration by surfactants may thus play an important role in the enhancement of foliar uptake of water-soluble herbicides such as glyphosate.     

Modelling penetration of plant cuticles by crop protection agents and effects of adjuvants on their rates of penetration

A theory of cuticular penetration of crop protection agents (CPAs) is presented, which incorporates properties of cuticles and cuticular waxes as well as properties of active ingredients and adjuvants. Based on this theory, two models are developed which are analytical in the sense that they help to quantify and understand (i) differences in permeability among cuticles from different species, (ii) effects of properties of CPAs on permeabilities of cuticles and rates of uptake and (iii) the effects of adjuvants on properties of cuticles and rates of uptake of CPAs. The models can be used to predict rates of uptake of CPAs as affected by properties of cuticular waxes, active ingredients and adjuvants. However, before this can be done, a constant, two parameters and at least two variables must be estimated. Properties of cuticles are accounted for by the constant D⁰/Δx and the parameter β′. The former, the ratio of the mobility of a hypothetical molecule having zero molar volume (D⁰x) divided by the path length (Δx) across the cuticle, has the dimension of velocity (ms^?1) and is independent of the solubility of the CPA. The latter is a measure of size selectivity of the cuticle. Differences in permeabilities of cuticles from different species increase with increasing size of active ingredients due to size selectivity (β′). Removing cuticular waxes from Citrus cuticles increased D⁰/Δx by a factor of 2042, while β was not affected. Differential solubility of CPAs is considered part of the driving force and at least two different partition coefficients are needed to account for differences in solubilities in cuticular waxes, cutin, water and the formulation residue on the surface of the cuticles. Adjuvants are solvents in the formulation residue on the leaf surface once the carriers (water and other volatile solvents) have evaporated and certain adjuvants also act as accelerators; they penetrate the cuticle and increase D⁰/Δx. Thus, accelerators increase rates of uptake and this effect depends on two factors, (i) the intrinsic activity of the accelerator and (ii) rate of penetration into the cuticle, because the active ingredients follow the accelerator front across the cuticle. Since accelerators penetrate from the formulation residue into the cuticle, the volume of the formulation residue decreases with time. This maintains high concentrations of CPAs in the formulation residue and, thus, maximum driving forces and rates of penetration. To utilise fully this dual accelerator effect, it is necessary to match velocities of penetration of accelerators and active ingredients accurately.     

Cuticular sorption and desorption of a nonionic diethylene glycol monooleate surfactant

Sorption and desorption of ‘Pegosperse’ 100-O(PEG 100-O; diethylene glycol monooleate, containing 15% diester) surfactant by unaltered (CM) and dewaxed (DCM) adaxial cuticle membranes isolated from apple (Malus pumila M.) leaves were studied. The aim of this study was to understand interactions between surfactants and cuticles. Enzymatically isolated cuticles were soaked in buffer or PEG 100-O solution (pH 7–0). and the weight changes of cuticles were measured to determine the amount of surfactant sorbed or desorbed by the cuticles. For very low surfactant concentrations, sorption was measured by changes in the surface tension of the solutions. PEG 100-O sorption by both the CMs and the DCMs occurred mainly in the first three hours and was concentration-dependent. The DCMs always sorbed more surfactant than the CMs. Desorption of PEG 100-O from both CMs and DCMs was rapid in the first few hours and then decreased to a relatively low rate until the surfactant was totally desorbed from the cuticles after about two months. The sorption and complete desorption of the surfactant by both CMs and DCMs show that PEG 100-O interacts with both cutins and waxes of the cuticles and the interactions are reversible.     

Effects of nonionic surfactants on cuticular sorption and penetration of 2, 4-dichlorophenoxy acetic acid

Surfactants increase the uptake of some foliar-applied chemicals to a greater extent than would be expected from their effects on surface tension and spray coverage. This study of the uptake of 2, 4-D [(2, 4-dichlorophenoxy)acetic acid] evaluated the effect of surfactants on penetration through and sorption by isolated cuticles of apple leaves. [¹⁴C]2, 4-D was placed in glass chambers affixed to enzymatically isolated adaxial apple leaf cuticles after the cuticle segments had been treated with various surfactants. The same surfactant pretreatments were included in sorption studies in which cuticle segments were immersed in [¹⁴C]2, 4-D for 96 h. Quantities of 2, 4-D passing through or sorbed by the cuticle were determined. Similar experiments were conducted with unaltered cuticles and cuticles dewaxed with chloroform. The hydrophile-lipophile balance (HLB) of polyethylene-glycol-based surfactants was inversely related to the sorption of those surfactants by the cuticles and penetration of 2, 4-D. Sorption of 2, 4-D by apple leaf cuticles was unaffected by surfactant pretreatment. Dewaxed cuticle membranes showed a similar response to 2, 4-D penetration and sorption following the surfactant pretreatment.     

Radiolabelling of isolated cuticles from foliar discs used as a test of cuticle biosynthesis

The radiolabelling of isolaled Hedera helix L, (ivy) leaf cutieles was investigated after incorporation of [¹⁴C]acetate in foliar discs Cuticle radioactivity greatly decreased as leaf age inereased. The percentage of radioactivity incorporated in the upper cuticles decreased from 0.5% to 0.08% of the total radioactivity of foliar dises from young to old leaves. Cuticle radioactivity was recovered in waxes, cutin and polar components. It was considerably greater for waxes when expressed in terms of cuticle mass. The methodology was validated using S-ethyl-dipropylthiocarbamate (EPTC). The radioactivity incorporation in cuticles was significanly reduced when 1 m m EPTC was deposited as a 20-μL droplet on lo foliar dises 6 h before the incorporation of radiolabelled acetate. EPTC inhibited radioiabelling of wax and cutin fractions in the upper and lower cuticles. Some acetylenic fatty acid analogues inactivating lauric and oleic acid ω-hydroxylases, used as acid and sulphonate forms in the same experimental conditions as EPTC, induced no reduction in cuticle radiolabelling. An inhibitory effect was observed only for the acetylenic and the saturated C₁₂ fatty acid analogues, used as tetrabu-tylammonium sulphonates, when applied directly in the liquid medium supporting foliar dises. Several assumptions are considered to explain the results of the present investigation.     

Sorption of low levels of nonionic and anionic surfactants on soil: effects on sorption of triticonazole fungicide

The sorption of two anionic surfactants and a series of seven nonionic alkylphenolethoxylate surfactants of increasing hydrophilic/lipophilic balance (HLB) in a loamy clay soil was evaluated. The effect of low doses of these surfactants on the sorption characteristics of the fungicide triticonazole was investigated. The critical micellar concentration (CMC) of the surfactants in pure water and soil–water systems, and surfactant sorption were estimated by surface tension measurements using a batch equilibration technique. Triticonazole sorption, alone and in the presence of low doses of surfactants, was also measured by batch equilibration. CMC of the alkylphenol surfactants increased with their HLB. The sorption of surfactants increased with their lipophilicity. CMC in the soil–water systems were considerably higher than in pure water. Sorption of the most lipophilic alkylphenol surfactants at the higher doses significantly increased triticonazole sorption. Proposed mechanisms are modifications of soil surface properties, and increase of soil organic carbon content. Sorption of the other nonionic and anionic surfactants only resulted in monomeric surfactant concentrations in pore water, and did not affect triticonazole sorption. © 1998 Society of Chemical Industry     

Effects of alcohols,glycols and monodisperse ethoxylated alcohols on mobility of 2,4-D in isolated plant cuticles

Effects of n-alcohols, ethoxylated alcohols and glycols on mobility of 2,4-dichlorophenoxy acetic acid (2,4-D) in cuticular membranes (CM) isolated from bitter orange (Citrus aurantium L.) leaves were studied. 1-Heptanol, 1-octanol and 1-nonanol had the highest effects, as they increased solute (2,4-D) mobility by 25- to 30-fold. Increasing the number of carbon atoms in the alcohols decreased their effectiveness. Ethoxylation of alcohols did not increase 2,4-D mobility and effectiveness decreased with increasing ethoxylation. Free glycols had no effect on solute mobility in isolated cuticles. The results show that ethoxylation is not required for increasing solute mobility in cuticles. It is suggested that alcohols and ethoxylated alcohols are sorbed in cuticular waxes and plasticize them. The data show that alcohols and ethoxylated alcohols having between seven and ten carbon atoms are powerful accelerator adjuvants, as long as the degree of ethoxylation is not too high. Free short-chain alcohols synthesized by leaves may act as endogenous plasticizers and modulate permeabilities of cuticles, depending on environmental and growing conditions.     

Polydisperse ethoxylated fatty alcohol surfactants as accelerators of cuticular penetration. 2: Separation of effects on driving force and mobility and reversibility of surfactant action

Polydisperse ethoxylated fatty alcohol (EFA) surfactants can improve the performance of crop protection agents. At the cuticular level they act as accelerators of penetration by increasing the mobility of active ingredients in the cuticle, the barrier properties of which are mainly caused by cuticular waxes. Polydisperse Genapol C-050 (GP C-050, average formula C12.5E5.8) was also found to increase mobility in wax-extracted polymer matrix membranes (MX) of bitter orange and pear, indicating that sorption of surfactants increased segmental mobility of polymethylene chains in cutin and wax. Sorption into MX of the active fraction of GP C-050 from 5g litre⁻¹ micellar solutions was in equilibrium in less than 1 h after establishing contact. This is almost 100-fold faster than with cuticular membranes (CM). Temperature dependence of solute mobilities in CM was studied in order to measure activation energies (E_D) of diffusion in the presence and absence of aqueous surfactant solutions. Monodisperse fatty alcohol ethoxylates C8E3, C8E4 and C12E6, and (non-surface-active) tributylphosphate decreased E_D of the model compounds WL 110547 and bifenox in Citrus, Pyrus and Stephanotis CM by more than 100 kJ mol⁻¹. This corresponds to 50 to 275-fold increases of mobilities at 15 °C. Our data suggest that the decrease in activation energies with the concomitant accelerating effect on mobility contributes considerably to the effects of so-called activator surfactants. High temperature and accelerators act similarly on barrier properties of CM. It is shown that effects of both monodisperse and polydisperse EFA surfactants on solute mobility are reversible and that radiolabelled C12E8 penetrated pear CM rapidly. However, rates of penetration were lowered by excess amounts of WL 110547 and especially phenylurea. Partition coefficients of seven organic solutes between Capsicum fruit cuticles and GP C-050 were very low and, with the exception of methylglucose, smaller than 1. They decreased with lipophilicity and differed about 100-fold. Especially for the lipophilic compounds they were orders of magnitude lower than octanol/water or cuticle/water partition coefficients, which indicates the limited usefulness of these values for an understanding of penetration of active ingredients from formulation residues. © 1999 Society of Chemical Industry     

The role of waxes in the uptake of metolachlor into sorghum in relation to the protectant CGA 43089

The grass weed herbicide metolachlor (2-chloro-N-[2-ethyl-6-methylphenyl]-N-[2-methoxy-1-methylethyl]acetamide) which is especially effective against wild millets, inhibits the formation of epicuticular waxes on sorghum leaves. The metolachlor protectant CGA 43089 [α - (cyanomethoximino) - benzacetonitrile] prevents the depletion of the waxes on the leaves of metolachlor-treated sorghum plants, as demonstrated by scanning electron microscopy. This alteration of the plant surface polymers also changes their permeability to the herbicide. ¹⁴C-metolachlor uptake into isolated coleoptiles and first leaves of sorghum which had been pretreated with the herbicide was increased. Incubation with added protectant reduced the uptake of ¹⁴C-metolachlor. It is postulated that the modifications caused by metolachlor and its protectant to sorghum surface structures influence the action of the herbicide in two ways:

• 1 The selectivity observed against sorghum and millet grasses could occur because of an increased uptake of metolachlor through cuticles which are particularly sensitive to the structural changes caused by the herbicide, since the composition of the plant waxes is very species-specific.
• 2 The loss of cuticular integrity is prevented by the protectant CGA 43089, which greatly reduces penetration of metolachlor.

     

Permeation of organic molecules of widely differing solubilities and of water through isolated cuticles of orange leaves

Water penetrated through isolated leaf cuticles of dwarf orange (Citrus mitis Blanco, ?Calamondin’?) as undissociated molecules because both [¹⁸O] water (¹H₂¹⁸O) and HTO (¹H³H¹⁶O) permeated at the same rate. HTO penetrated to 3 to 21% of the theoretical equilibrium value (TEV) in an unstirred system within 10 days for astomatous cuticles and 50 to 60% of TEV for stomatous cuticles. The permeability coefficient (k) of HTO through astomatous cuticles at 25°C was 6.8 × 10^?7 cm s^?1. Two highly water-soluble ¹⁴C-labelled compounds, trichloroacetic acid (TCA) and 1,2,4-triazol-3-ylamine [aminotriazole (BSI) or amitrole (ISO)], and two nearly water-insoluble ¹⁴C-labelled compounds, 1-naphthyl methylcarbamate (carbaryl) and 2,6-dichloro-4-nitroaniline (dicloran), were compared to HTO as a reference standard in permeation studies. All four organic molecules permeated without decomposing. The relative k values for TCA, aminotriazole, carbaryl, HTO and dicloran were 0.32, 0.47, 0.71, 1.0, and 1.5 respectively. Although this suggested that the permeation of organic molecules may be inversely related to water solubility, this could not be established with certainty due to large variations in the data. The k values were obtained for 12 other organic compounds through a variety of biological and model membranes or were calculated from the literature. Any relationships between k and various molecular characteristics were unclear because a wide variety of cuticle sources and experimental design was used by different investigators working in this area. The calculation of k is considered essential in all permeability studies so that comparisons can be made between laboratories.     

Concentration-Dependent Mobility of Chlorfenvinphos in Isolated Plant Cuticles

The mobility of chlorfenvinphos in isolated pear (Pyrus communis cv. Bartlett) leaf cuticular membranes (CM) was studied as a function of concentration of chlorfenvinphos sorbed in the cuticle. Mobilities of chlorfenvinphos increased approximately 9-fold when the amount sorbed increased from 1 to 100 μg cm⁻² pear leaf cuticle. From the amounts per area, average volume fractions of chlorfenvinphos in the cuticle were calculated ranging from 2×10⁻³ to 5·1×10⁻². The increase in mobilities was steepest at the lower and levelled off at higher volume fractions. This correlation could be described for the whole range of volume fractions investigated by an equation which assumes homogeneously dispersed chlorfenvinphos. Temperature dependence of mobilities was studied at 17, 25 and 35°C and chlorfenvinphos volume fractions of 5·5×10⁻³ and 0·12, respectively. Arrhenius graphs were linear for both volume fractions, showing that cuticles did not undergo a phase transition due to the high amount of sorbed chlorfenvinphos. However, at a volume fraction of 0·12, the activation energy of diffusion, E_D, was significantly lower (83·6 kJ mol⁻¹) than at 5·5×10⁻³ (135 kJ mol⁻¹). We interpret these findings as evidence for a plasticising effect on cuticular waxes by chlorfenvinphos. So far, such an effect had been demonstrated only for certain adjuvants (ethoxylated alcohols) but not for active ingredients. Chlorfenvinphos not only increased its own mobility in pear leaf cuticles, but also that of 2,4-D in Citrus leaf cuticles. This would be expected if plasticising of waxes was the sole mechanism responsible for increased mobilities. From these data we predict that permeabilities of cuticles to chlorfenvinphos are not constant. Depending on temperature as well as types and amounts of adjuvants, rates of foliar penetration of chlorfenvinphos can be higher if its concentration in the spray liquid is increased.     

降雨及助剂对咪唑乙烟酸药效的影响

以苘麻Abutilon theophrasti为测试植物,研究了施药后降雨和助剂对咪唑乙烟酸除草活性的影响。结果表明,咪唑乙烟酸有较好的耐雨性,药后2 h内无降雨,可保持相当的防效,药后4~8 h内无降雨,与无降雨的没有显著差异。添加非离子表面活性剂能明显提高咪唑乙烟酸的除草活性。其中增效作用从大到小依次为:AM-100＞PPJ-15＞OP-10＞SDP,咪唑乙烟酸的IC50值分别比未加助剂处理的下降了33.6%、35.4%、29.5%和17.1%。咪唑乙烟酸的用量越低,助剂的增效作用越明显。     

Finite dose diffusion studies: I. Characterizing cuticular penetration in a model system using NAA and isolated tomato fruit cuticles

A finite dose diffusion system was employed to study cuticular penetration of 2‐(1‐naphthyl) [1−¹⁴C]acetic acid (NAA) from simulated spray droplets through enzymatically isolated tomato fruit cuticles (Lycopersicon esculentum Mill cv Pik Red). Isolated cuticles were mounted on diffusion half‐cells with the cell wall surfaces facing a 20 mM citric acid receiver solution (pH 3.2, volume 2.9 ml, prepared with deionized water). A 5‐µl donor droplet containing NAA at 100 µM in 20 mM citric acid buffer (pH 3.2) was applied to the outer surface. Penetration was monitored by repeated sampling of the receiver solution. NAA penetration was characterized by (1) an initial lag phase of about 2.3 h, (2) a phase of nearly constant maximum rate of penetration averaging 6.3% of applied NAA h⁻¹ (equivalent to 0.032 nmol h⁻¹) and (3) a plateau phase approaching an asymptote at 81.2% of applied NAA (equivalent to 0.406 nmol) at 120 h. Within 1 h after application droplets appeared dry on visual inspection. Immediately after droplet drying, 7.0% of the applied NAA was sorbed to the cuticle, but only 0.5% penetrated into the receiver solution, indicating that penetration occurred almost exclusively from the apparently dry deposit. At 120 h, 5.2% of the NAA applied was associated with the deposit and 4.3% with the cuticle. The distribution of maximum rates of penetration was log‐normal, but penetration at 120 h followed a normal distribution. Cuticle thickness (estimated 5–25 µm) had no significant effect on NAA penetration. Maximum rates of penetration through pepper fruit and citrus and ficus leaf cuticles were 4.9‐, 2.6‐ and 0.1‐times that through tomato fruit cuticles. At 120 h, penetration averaged 85.5, 79.5 and 34.7% for pepper, citrus and ficus cuticles, respectively. Extracting epicuticular and embedded waxes increased NAA penetration rates through tomato fruit cuticle more than three‐fold, but had little effect on penetration at 120 h (71.0 vs 87.7% for cuticular vs dewaxed cuticular membranes). The maximum penetration rate and total penetration were found to be useful parameters in describing the penetration time‐course. © 2000 Society of Chemical Industry     

Biological implications of the use of surfactants in medicines: and the biphasic effects of surfactants in biological systems

A survey of the biological effects of surface-active agents reveals that their affinity for membranes and in particular their ability to penetrate and increase the permeability of membranes is of prime importance. An increase in drug absorption from the gastrointestinal tract, from muscle, from the rectum and from topical preparations is frequently a result of an increase in membrane permeability; the effect of surfactants on enzyme activity can be also the result of changes in organelle permeability or to surfactant-induced changes in protein conformation. As anionic surfactants and cationic surfactants tend to exhibit too high a degree of toxicity, non-ionic agents are most commonly used in pharmaceuticals. Experiments to elucidate the mode of action of a range of commercially available non-ionic surfactants on the increase in drug absorption in model systems employing goldfish (Carassius auratus) are described. Emphasis is placed on the biphasic effects of the surfactants whereby an increase in membrane permeability is observed at low concentrations (frequently below the critical micelle concentration of the surfactant) and a decrease in overall absorption is found at higher concentration. Such biphasic effects are frequently encountered in the literature on surfactant effects in biological systems.     

Cuticular penetration of 2,4-D as affected by interaction between a diethylene glycol monooleate surfactant and apple leaf cuticles

Impacts of pH and sorption-desorption of ‘Pegosperse’ 100-O (PEG. 100-O; diethylene glycol monooleate, containing 15% diester) surfactant by apple (Malus pumila M.) leaf cuticles on surfactant-enhanced cuticular penetration of 2,4-D [(2,4-dichlorophenoxy)acetic acid] were studied. Glass cylinders were affixed to enzymatically isolated adaxial apple leaf cuticles after the cuticle segments had been soaked in 10 ml liter^?1 PEG 100-O solution and washed for 20 and 120 min, respectively. Quantities of [¹⁴C]2,4-D in the glass-cuticle chambers passing through the cuticles at pH values from 1 to 6 5 were determined. PEG 100-O significantly increased cuticular penetration of dissociated 2,4-D at pH 4–5; the surfactant had no effect on penetration of undissociated 2,4-D at pH 10. Surfactant-enhanced penetration of 2,4-D occurred only when the surfactant was in the cuticles, while the process of surfactant sorption-desorption alone had no effect on penetration. These results support a ‘hydrophilic channel’ hypothesis, i.e. that surfactants may create hydrophilic channels or increase the area of the channels in the cuticle and, consequently, enhance the passing of polar molecules like dissociated 2,4-D through the cuticle.     

Behaviour of famoxadone deposits on grape leaves

Famoxadone is a new fungicide developed for the control of crop diseases, including grape downy mildew (Plasmopara viticola). The majority (>90%) of the spray deposit from a famoxadone 500 g kg⁻¹ water‐dispersible granule formation on a grape leaf were found on the leaf surface or associated with epicuticular waxes. A significant fraction of this deposit could not be removed by a water wash, suggesting strong binding to the waxes. Nearly 100% of the spray deposit was still recovered after 12 days of exposure to a dry environment, confirming the good residual properties of the substance. Thirty per cent of the applied active ingredient was lost after exposure to a wet environment, probably via hydrolysis or wash‐off. Studies with radiolabelled famoxadone formulated as a suspension concentrate indicated that redistribution occurred both in dry conditions, via diffusion in the cuticular waxes, and in wet conditions via dissolution in water followed by re‐deposition. No systemic movement of famoxadone was observed within the treated plant. Grape plants treated with famoxadone alone or in mixture with cymoxanil and subjected to up to 50 mm of artificial rain remained well protected against downy mildew infections. Good rain‐fastness was observed even 2 h after fungicide application. Despite low water solubility, famoxadone spray residues on grape leaves were reactivated in surface water sufficiently quickly to prevent infection by P viticola. © 2000 Society of Chemical Industry     

Effect of some ethoxylated alkylphenols and ethoxylated alcohols on the transfer of [14C] chlorotoluron across isolated plant cuticles

The effect of several ethoxylated octylphenols (OP), nonylphenols (NP) and alcohols (AA) on the penetration of [¹⁴C]chlorotoluron through isolated box-tree (Buxus sempervirens L.) leaf cuticles was investigated. The herbicide solution was deposited as droplets onto cuticle discs maintained on agar blocks acting as receivers. The effects on chlorotoluron transfer across the cuticles depended on the degree of ethoxylation of the surfactant. For each series, the chlorotoluron transfer was considerably increased by surfactants with low ethylene oxide (EO) content (3 to 6 EO). This effect appeared 24 h after droplet application, then increased with time. It decreased with further increase in the ethoxylation number, and surfactants with a long ethylene oxide chain (OP16, NP20, NP40 and AA20) had no effect. Surfactant concentration (OP5) had a large influence on chlorotoluron transfer; penetration increased sevenfold when OP5 concentration was raised from 0.01 to 10 g l^?1. Diffusion of the two tritiated octylphenols, [3H]OP5 and [3H]OP16, was measured simultaneously during chlorotoluron transfer. The diffusion rate of the two surfactants across the cuticles was similar, but a higher amount of OP5 was retained within the cuticle during transfer. Study of the effect of surfactants on the cuticular waxes using differential scanning calorimetry showed that wax begins to melt at a lower temperature in the presence of the nonylphenols NP9 and NP4. Fusion enthalpy was close to -30 J g^?1. Effet de quelques alkylphénols et alcools éthoxylés sur la pénétration du [¹⁴C]chlortoluron à travers des cuticules végétales isolées Nous avons testé l'effet de plusieurs octylphénols (OP), nonylphénols (NP) et alcools éthoxylés (AA) sur la pénétration du [¹⁴C]chlortoluron à travers des cuticules isolées de feuilles de buis. L'herbicide en solution était déposé sous forme de gouttelettes sur des disques de cuticules plaées sur agar. Les effets observés dépendaient du degré d'ethoxylation du surfactant. Pour chaque série, le transfert du chlortoluron à travers les cuticules était considérablement accru avec les surfactants faiblement éthoxylés (3 à 6 oxydes d'éthylène). Cet effet apparaissait 24 h après l'application des gouttelettes puis augmentait avec le temps. Il diminuait avec l'accroissement du nombre d'éthoxylation et aucun effet n'était observé avec les surfactants à longue chaine d'oxydes d'éthylène (OP16, NP20, NP40 et AA20). La concentration en surfactant (OP5) avait une grande influence sur le transfert du chlortoluron dans l'agar, il augmentait sept fois entre 0.01 et 10 g l^?1. La diffusion des deux octylphénols (³H-OP5 et ³H-OP16) a été mesurée simultanément durant le transfert du chlortoluron. La vitesse de diffusion des deux surfactants à travers les cuticules était comparable, mais une quantité plus élevée d'OP5 était retenue dans les cuticules durant le transfert. L'étude par analyse calorimètrique à balayage de l'effet des surfactants sur les cires cuticulaires a montré que la fusion des cires commence à plus faible température en présence des nonylphénols NP9 et NP4. L'enthalpie de fusion était en général voisine de -30 J g^?1. Wirkung einiger ethoxylierter Alkylphenole und Alkohole auf den Transfer von [¹⁴C]Chlortoluron durch die Pflanzen-Cuticula Die Wirkung verschiedener ethoxylierter Octylphenole (OP), Nonylphenole (NP) und Alkohole (AA) auf die Penetration von [¹⁴C]Chlortoluron durch die isolierte Blatt-Cuticula von Buxbaum (Buxus sempervirens L.) wurde untersucht. Die Herbizidlösung wurde als Tröpfchen auf Cuticula-Scheiben, die auf Agarblöcken als Empfänger ausgelegt worden waren, ausgebracht. Die Wirkung auf den Chlortoluron-Transfer durch die Cuticula hing von der Ethoxylierung des Zusatzstoffes ab. In allen Serien wurde der Transfer durch Zusatzstoffe mit niedrigem Gehalt an Ethyloxiden (EO) erheblich gesteigert (3 bis 6 EO). Diese Wirkung trat 24 h nach der Applikation der Tröpfchen ein und nahm dann mit der Zeit zu. Mit dem Anstieg der Ethoxylierungszahl nahm die Wirkung ab, und Zusatzstoffe mit einer langen Ethylenoxidkette (OP16, NP20, NP40 und AA20) waren wirkungslos. Die Konzentration des OP5-Zusatzstoffes hatte großen Einfluß auf den Chlortolurontransfer; die Penetration war versiebenfacht, wenn die OP5-Konzentration von 0,01 auf 10 g l^?1 angehoben wurde. Die Diffusion der Octylphenole [³H]OP5 und [³H]OP16 wurde während des Chlortolurontransfers gemessen; die Diffusionsrate war ähnlich, aber von OP5 wurde ein größerer Anteil in der Cuticula zuückgehalten. Die Wirkung der Zusatzstoffe auf das Cuticularwachs wurde calorimetrisch untersucht, und es zeigte sich, daß das Wachs in Gegenwart der Nonylphenole NP9 und NP4 bei niedriger Temperatur zu schmelzen beginnt. Die Fusionsenthalpie lag bei -30 J g^?1     

表面活性剂、喷液量及杂草叶角对普杀特喷后附着量的影响

表面活性剂、喷液量及杂草叶角对普杀特在非敏感杂草马唐叶片上的喷后附着量有明显的独立影响和交互影响,其中表面活性剂的影响最大。供试的6种非离子型表面活性剂均因显著降低了普杀特药液的表面张力从而显著提高了其在马唐叶片上的喷后附着量,其中ScOil和Silwet—L77对其提高幅度最大;普杀特在马唐叶片上的喷后附着量随着喷液量的减少逐步增加,但在0—90°范围内随着马唐叶角的减小而减少,其由于喷液量的增大或马唐叶角的减小而引起的下降量,可通过加入非离子型表面活性剂而得到补偿,加入非离子型表面活性剂配合下午微液量(90L/ha)喷施,可望最大限度地增加普杀特在其非敏感杂草叶片上的喷后附着量,进而提高其药效,降低其使用成本和减少其在土壤中的残留。     

Modelling the effects of alcohol ethoxylates on diffusion of pesticides in the cuticular wax of Chenopodium album leaves

Cuticular waxes represent the first and, in most cases, the limiting barrier for foliar uptake of pesticides from solution. Sorption of pesticides in reconstituted cuticular wax (wax/water partition coefficients) of Chenopodium album L. and in isolated cuticular membranes (cuticle/water partition coefficients) of Prunus laurocerasus L. was determined. Diffusion coefficients of pesticides in reconstituted cuticular wax of C. album leaves were size-dependent, increasing with increasing molar volume. In the presence of alcohol ethoxylates, diffusion coefficients were enhanced by up to two orders of magnitude, and size selectivity was significantly decreased. The accelerating effect and the decrease in size selectivity were attributed to plasticisation of the cuticular wax by the alcohol ethoxylates increasing the fluidity in the wax. A free volume model adopted from polymer science was successfully applied to predict diffusion coefficients of pesticides on the basis of the transport properties of the wax (size selectivity and crystallinity), the molar volume of the diffusing compound and the accelerator concentration in the wax.     

Penetration of triolein and methyl oleate through isolated plant cuticles and their effect on penetration of [14C]quizalofop-ethyl and [14C]fenoxaprop-ethyl

The penetration of two model seed oil compounds, [¹⁴C]triolein (TRI) and [¹⁴C]methyl oleate (MEO) through plant cuticles and their effects on the penetration of [¹⁴C]quizalofop-ethyl and [¹⁴C]fenoxaprop-ethyl were investigated. Experiments were carried out using isolated cuticles from rubber plant (Ficus elastica Roxb.) leaves and from tomato (Lycopersicon esculentum Mill,) and pepper (Capsicum annuum L.) fruits. Chemicals were deposited in droplets on to cuticle discs maintained on agar blocks under controlled conditions. TRI and MEO were used at 1% (V/V). The transfer of radiolabel through cuticles was negligible for TRI and varied from 6 to 13% after 72 h, according to species, for MEO, The penetration results obtained for quizalofop-ethyl (0.084 mg mL^-1) and fenoxaprop-ethyl (0.189 mg mL^-1) were very similar and varied according to species. The greatest diffusion intoagar was observed for pepper (12.8% and 10.7% after 72 h, for quizalofop-ethyl and fenoxaprop-ethyl respectively), the lowest for rubber plant cuticles (1.4 and 1.3% respectively). Addition of MEO produced significant increases in the penetration of quizalofop-ethyl and fenoxaprop-ethyl through rubber plant and tomato cuticles. TRI had an enhancing effect on the two herbicides only with rubber plant cuticles. Results are discussed with particular consideration of the variations between plant species and the possible mode of action of seed oil adjuvants.