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     

Reinvestigating adjuvants for the wild oat herbicide,flamprop-M-isopropyl. I: Glasshouse trials

Commercial formulations of flamprop-M-isopropyl and formulations of other members of this class of herbicide have always contained an oil adjuvant to increase herbicidal performance. Further increases of performance could be obtained by following the label recommendations to add further quantities of a commercial emulsifiable oil (e.g. ‘Swirl’). Nevertheless it was judged that, in view of current advances in adjuvant research, even greater improvements in herbicidal performance could be obtained with different types of adjuvants. Experimental trials using a cultivated oat (Avena sativa L.) assay under glasshouse conditions to test ranges of surfactants (alkyl aryl, alkyl saccharide, alkylamine and alcohol ethoxylates) and emulsifiable oils (paraffinic/naphthenic, rape seed, transmethylated rape seed) showed that all of these adjuvants were capable of increasing flamprop-M-isopropyl activity compared with that of an emulsifiable concentrate formulation containing no adjuvant. Alkylamine and alcohol ethoxylates, with no particular preference for the length of the alkyl chain, but optimum ethylene oxide content of 5 moles and 7–10 moles respectively, were the most efficacious and better than the current emulsifiable oil system. There was no additional benefit from mixture of these two types of adjuvant and an alcohol ethoxylate (‘Dobanol’ 25-7) was preferred on cost grounds. This adjuvant also gave substantial activity to the otherwise inactive suspension concentrate formulation. Final trials determined that the optimum application rate of ‘Dobanol’ 25–7 was in the range 1000–1500 g ha^?1, and this information guided the design of subsequent field trials.     

Mobilities of Organic Compounds in Reconstituted Cuticular Wax of Barley Leaves: Effects of Monodisperse Alcohol Ethoxylates on Diffusion of Pentachlorophenol and Tetracosanoic Acid

Effects of monodisperse alcohol ethoxylates on mobilities of ¹⁴C-labelled pentachlorophenol (PCP) and tetracosanoic acid (C₂₄AC) in reconstituted cuticular wax of barley leaves were measured. Depending on the respective alcohol ethoxylate investigated, the diffusion coefficient (D) of PCP in barley wax was increased by factors ranging from 3·3 to 19·6, whereas D of C₂₄AC, was increased by factors varying between 22 and 315. In order to analyse the relationship between the concentration of surfactants in the wax and their effects on D, the amounts of alcohol ethoxylates dissolved in the wax at equilibrium with external concentrations well above the critical micelle concentration (CMC) were determined. Wax/water partition coefficients (K_ww) of the alcohol ethoxylates were about one order of magnitude lower than cuticle/water partition coefficients (K_cw), which is a consequence of the semi-crystalline structure of the wax compared with amorphous cutin. Correlations between effects on D and maximum amounts of alcohol ethoxylates dissolved in the wax were obtained indicating an unspecific wax/surfactant interaction. This was solely dependent on the amount of surfactant sorbed to the wax, leading to increased mobilities of pesticides in the wax. Applying ESR-spectroscopy, which gave an insight into the molecular structure of the wax, supported this interpretation of an unspecific plasticising effect of the alcohol ethoxylates on the molecular structure of the wax. The results obtained in this study are in good accordance with the results obtained in a recent study investigating the effects of the same group of alcohol ethoxylates on mobilities of pesticides in isolated, but intact, cuticular membranes of Citrus. This demonstrates that the investigation of isolated and subsequently reconstituted cuticular wax is a useful model system analysing the mechanisms of the surfactant interaction with the transport-limiting barrier of plant cuticles.     

STRUCTURE-ACTIVITY RELATIONSHIPS OF ALKYL- PHENOL ETHYLENE OXIDE ETHER NON-IONIC SURFACTANTS AND THREE WATER-SOLUBLE HERBICIDES

Summary. Several alkylphenol ethylene oxide ether non-ionic surfactants were tested in aqueous foliar sprays with dalapon, amitrole and paraquat for (heir enhancement of phytocidal activity against Zea mays L. With three homologous series of surfactants studied (octyl-, nonyl- and laurylphenol types), the herbicide, the surfactant concentration and the hydrophilic constitution (ethylene oxide content) of the surfactant molecule all markedly influenced maximum toxicity. Smaller apparent differences in effectiveness were also attributable to the hydrophobic (alkylphenol) portion of the surfactant. The results arc discussed in relation to possible cuticle-spray solution interactions and their influence on herbicide penetration.
Relations entre la structure et l'activite de produits tensio-actifs non ionigues, a base d'éther d'oxyde éthylénique et d'alkylphénol, en présence de trois herbicides hydrosolubles     

Effects of adjuvants on the performance of a novel powdery mildew fungicide, 1-(4-chlorobenzyl)-4-phenylpiperidine

The effects of adjuvants on the performance of a dispersible concentrate formulation (DCI) of a novel powdery mildew fungicide, 1-(4-chlorobenzyl)-4-phenylpiperidine (I) were investigated. The method involved assessment, under glasshouse conditions, of the therapeutic (curative) control of infections of powdery mildew (Erysiphe graminis DC f.sp. hordei Marchal) on barley (Hordeum vulgare, L.) eight to nine days after spray application to plants that had been inoculated one day prior to spraying. The results from the first trial showed that marked improvements (∽five-fold) in the performance of DCI could be obtained by the spray tank addition of some types of surfactant adjuvants and a series of further trials investigating a wide range of adjuvants was conducted. Nonylphenol, alkylamine and alcohol ethoxylates varying in mean ethylene oxide content between 5 and 20 moles were highly effective. There were indications that optimum performance enhancements were obtained with these surfactants containing between 5 and 10 moles ethylene oxide. Lower enhancements, sometimes only marginal, were obtained from trisiloxane, phosphate ester, propylene oxide, alkylamine-propylene oxide and castor oil ethoxylates and also alkyl polyglucoside biosurfactants. Negligible adjuvant enhancements were observed with emulsifiable paraffinic/naphthenic and rape seed oils, though slightly better enhancements were seen with an emulsifiable transmethylated rape seed oil and, interestingly, larger enhancements with an emulsifiable lipophilic alcohol. A final trial identified the alcohol ethoxylate, ‘Dobanol’ 91-6, as the most effective adjuvant and that its optimum application rate under glasshouse conditions was 250 g ha^-1. This information will be used to guide the design of field trials. © 1997 SCI     

Effect of Adjuvants on the Therapeutic Activity of Dimethomorph in Controlling Vine Downy Mildew. I. Survey of Adjuvant Types

The effect of adjuvants on the performance of emulsifiable concentrate (EC) and wettable powder (WP) formulations of dimethomorph, a new systemic Oomycete fungicide, has been investigated using a two-day therapeutic (curative) assay with downy mildew (Plasmopara viticola, Berl. & de T.) on vines (Vitisvinifera L., cv. Cabernet Sauvignon) in glasshouse trials. The EC formulation had some therapeutic activity in this type of test. This activity was increased by the spray tank incorporation of 6 g litre⁻¹ of either emulsifiable rape seed oil (‘Atplus’ 412) or emulsifiable paraffinic oil (‘Atplus’ 411F). However, these improvements in performance were overshadowed by those brought about by incorporation of 3 g litre⁻¹ of a series of C₁₃/C₁₄ alcohol ethoxylates varying in ethylene oxide content from 5 to 20 moles:(‘Marlipal’ 34/6EO, 34/11EO, 34/20EO). Nearly complete fungal control was obtained in the presence of these adjuvants with a dimethomorph application rate of 25 g ha⁻¹ compared with only around 90% control at 400 g ha⁻¹ without adjuvants. The WP formulation was inactive in this therapeutic test but the presence of the adjuvants improved the performance of this formulation towards the high levels observed with the EC plus adjuvants, demonstrating that adjuvants could markedly influence the performance of solid, otherwise therapeutically inactive, dimethomorph formulations. Further trials examined other types of adjuvants (nonylphenol, alkylamine and silicone ethoxylates) but either they were no better than the alcohol ethoxylates or they induced unacceptable phytotoxicity. Trials with alcohol ethoxylates (‘Genapols’) from another source demonstrated activity equivalent to the ‘Marlipal’ surfactants. A two-factorial matrix experiment with ‘Genapol’ C050 showed that, under glasshouse conditions, >90% control could be obtained with the dimethomorph EC at 25 g AI ha⁻¹ with 375 g ha⁻¹ ‘Genapol’ C050. Applications of the WP formulation required slightly higher rates of either 50 g AI ha⁻¹ plus 375 g ha⁻¹ ‘Genapol’ C050 or 25 g AI ha⁻¹ plus 750–1500 g ha⁻¹ ‘Genapol’ C050. The overall conclusion was that alcohol ethoxylates varying in alkyl chain length from C₁₂ to C₁₈ and ethylene oxide content between 5 and 20 moles for the C₁₂ surfactants and ∽15 moles for the C₁₈ surfactants were effective adjuvants in promoting the therapeutic activity of dimethomorph formulationsagainst P. viticola on glasshouse-propagated vines.     

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.     

Effect of adjuvants on the performance of the new cereal fungicide,metconazole. I glasshouse trials

Metconazole, (1RS, 5RS; 1RS, 5SR)-5-(4-chlorobenzyl)-2,2-dimethyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, is a highly active fungicide, in particular controlling seed-borne and foliar diseases of cereals, such as wheat (Triticum aestivum L.) and barley (Hordeum vulgare L.). In order to maximize its foliar activity, an experimental survey of some types of surfactants and an emulsifiable oil was undertaken. Two types of metconazole formulation were investigated using a biological assay involving the therapeutic control of two diseases (Erysiphe graminis DC f. sp. tritici Marchal and Leptosphaeria nodorum Muell.) of wheat. Enhancements of activity by ?Genapol’? C12/C14 alcohol ethoxylates of an emulsifiable concentrate (ECM) formulation of metconazole were approximately three- to four-fold. For its, initially, less active suspension concentrate (SCM) formulation, enhancements were around 35-fold, so that with these adjuvants the two formulations were of similar activity. The enhancement ability of these ?Genapol’? surfactants was optimal at lower (5–10 moles) ethylene oxide content. These analogues induced marginally better enhancements of activity than members of a range of nonylphenol ethoxylates (?Arkopal’?), and emulsifiable paraffinic/naphthenic oil (HVI 60E) and a castor oil ethoxylate (?Atlas’? G1281) but were equivalent to a similar series of alcohol ethoxylates (?Dobanol’?) from another source. Varying the alkyl chain length between C₉-C₁₁ and C₁₄-C₁₅ in the ?Dobanol’? series had little effect on their high enhancements of metconazole activity. It was determined from trials varying the application rate of the best alcohol ethoxylates that application rates of 1–1.5 kg ha^?1 were required for maximum activity. This implied the use of high adjuvant/metconazole ratios in one-pack adjuvant-containing formulations. A range of soluble liquid (SL) formulations were prepared with either ?Dobanol’? 23–6.5 or ?Dobanol’? 91-6/metconazole ratios varying from 5:1 to 15:1. There were found to be highly active and were recommended for field testing.     

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.     

Effect of additives in aqueous formulation on the foliar uptake of dimethomorph by cucumbers

BACKGROUND: The efficacy enhancement of dimethomorph formulation by several adjuvants is thought to be through increased foliar uptake. In order to identify the most effective adjuvants, the adjuvancy of 36 additives was examined in aqueous formulations in relation to the absorption of dimethomorph by cucumber leaves. RESULTS: Polyethylene glycol monohexadecyl ethers with ethylene oxide (EO) contents of between 7 and 20, polyethylene glycol monooctadecyl ethers with EO contents of between 10 and 20 and polyethylene glycol monooctadecenyl ethers with EO contents of between 6 and 20 were effective adjuvants for promoting dimethomorph uptake from both aqueous acetone solutions and aqueous wettable powder (WP) suspensions into cucumber leaves. Polyethylene glycol monododecyl ethers with EO contents of between 7 and 9 were effective in promoting dimethomorph uptake from aqueous WP suspensions but less effective relative to the other adjuvants tested with aqueous acetone solutions. Foliar uptake of dimethomorph was also facilitated by the addition of methyl hexadecanoate, methyl octadecenoate and methyl octadecadienoate. CONCLUSIONS: Although the foliar uptake of dimethomorph from both aqueous WP suspensions and aqueous acetone solutions was greatest in the presence of fatty alcohol ethoxylates generally having a C₁₆ or C₁₈ lipophile, uptake from aqueous surfactant–acetone solutions was, on average, 7.6‐fold greater than that from aqueous WP suspensions containing surfactant. Copyright © 2009 Society of Chemical Industry     

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.     

烷基糖苷和单烷基磷酸酯钾盐在3%甲氨基阿维菌素苯甲酸盐微乳剂中的应用及其环境安全性

为探讨绿色表面活性剂烷基糖苷(APG)和单烷基磷酸酯钾盐(MAPK)在3%甲氨基阿维菌素苯甲酸盐(简称甲维盐)微乳剂中的应用,以传统表面活性剂辛基酚聚氧乙烯醚(OP-10)和壬基酚聚氧乙烯醚磷酸酯(NP-10P)作对照,在运用拟三元相图法确定最佳复配比例的基础上,比较了MAPK/APG复配体系和NP-10P/OP-10复配体系对甲维盐的增溶作用;在表面活性剂总质量分数为10%及最佳复配比例下,分别采用2种表面活性剂复配体系制备了技术质量指标符合标准的3%甲维盐微乳剂,并测定了其对小菜蛾 Plutella xylostella 的生物活性;就绿色表面活性剂和传统表面活性剂对环境的安全性(对水生生物的安全性和生物降解性)进行了比较。结果表明:在最佳复配比例下,MAPK/APG[m(MAPK) :m(APG)=2 :1]的表面活性及对甲维盐的增溶能力均低于NP-10P/OP-10[m(NP-10P) :m(OP-10)=1 :2];用2种表面活性剂复配体系制备的微乳剂对小菜蛾的生物活性无明显差异;4种表面活性剂对斑马鱼和大型溞的毒性趋势相似——APG毒性最小,MAPK和NP-10P的毒性相当,OP-10毒性最大;28 d后APG、MAPK、NP-10P和OP-10的生物降解率分别为61.5%、49.7%、17.9%和15.0%,MAPK和APG的生物降解率明显高于NP-10P和OP-10。表明绿色表面活性剂APG和MAPK在农药制剂领域具有较好的开发应用前景。     

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 uptake of surfactants into wheat

The time course of uptake has been determined for seven poly(oxyethylene) surfactants, and one anionic surfactant (sodium dodecyl sulphate), into the leaves of wheat plants grown in a phytotron. Uptake was relatively rapid during an initial period of 24 h for six of the eight surfactants; after this period, the uptake rate was lower, and total uptake after 48 h was in the range 80-91% for those six surfactants. The other two compounds, sodium dodecyl sulphate and cetostearyl alcohol-22EO condensate (hexadecan-1-ol/octadecan-1-ol ethylene oxide condensate; average number of ethylene oxide units 22) were barely taken up at all. The observed time course for uptake was consistent with a complex process based on more than one rate-determining process. The physical properties of the surfactants are discussed in relation to their observed uptake behaviour. The surfactant deposit areas, measured by microscopy, were concluded to be not particularly relevant in interpreting the uptake results. Uptake was not related to surfactant chain length, but the physical form of the hydrated surfactant on a leaf surface appeared to influence uptake behaviour.     

Surfactant-enhanced foliar uptake of some organic compounds: Interactions with two model polyoxyethylene aliphatic alcohols

Interactions occurring during the surfactant-enhanced foliar uptake of seven model organic compounds were examined using two homogeneous surfactants, hexaethylene glycol monotridecyl ether (C13E6) and hexadecaethylene glycol monododecyl ether (C12E16). Surfactant–compound and compound–surfactant interactions were detected by measurement of their relative uptake rates following application of c. 0·2 μl droplets of the corresponding radiolabelled formulations. The magnitude of surfactant–compound interaction was found to vary according to the physicochemical properties of both the compound and the surfactant, and was influenced by surfactant concentration and target plant species. Interactive and non-interactive mechanisms, both leading to substantial enhancement of compound uptake, could be identified, but their precise nature could not be elucidated. Although penetration of C13E6 into the site of application appeared to be essential in order to activate the uptake of a compound, substantial absorption of C12E16 was not always required to produce the same effect. The results are discussed in the light of possible sites and modes of action for activator polyoxyethylene surfactant adjuvants.     

Some physicochemical factors influencing foliar uptake enhancement of glyphosatemono(isopropylammonium) by polyoxyethylene surfactants

Structure-concentration–foliar uptake enhancement relationships between commercial polyoxyethylene primary aliphatic alcohol (A), nonylphenol (NP), primary aliphatic amine (AM) surfactants and the herbicide glyphosatemono(isopropylammonium) were studied in experiments with wheat (Triticum aestivum L.) and field bean (Vicia faba L.) plants growing under controlled-environment conditions. Candidate surfactants had mean molar ethylene oxide (EO) contents ranging from 5 to 20 and were added at concentrations varying from 0·2 to 10 g litre^?-1 to [¹⁴C]glyphosate formulations in acetone–water. Rates and total amounts of herbicide uptake from c. 0·2–μl droplet applications of formulations to leaves were influenced by surfactant EO content, surfactant hydrophobe composition, surfactant concentration, glyphosate concentration and plant species, in a complex manner. Surfactant effects were most pronounced at 0·5 g acid equivalent (a.e.) glyphosate litre^?-1 where, for both target species, surfactants of high EO content (15–20) were most effective at enhancing herbicide uptake: surfactants of lower EO content (5–10) frequently reduced, or failed to improve, glyphosate absorption. Whereas, at optimal EO content, AM surfactants caused greatest uptake enhancement on wheat, A surfactants gave the best overall performance on field bean; NP surfactants were generally the least efficient class of adjuvants on both species. Threshold concentrations of surfactants needed to increase glyphosate uptake were much higher in field bean than wheat (c. 2 g litre^?-1 and < 1 g litre^?-1, respectively); less herbicide was taken up by both species at high AM surfactant concentrations. At 5 and 10 g a.e. glyphosate litre^?-1, there were substantial increases in herbicide absorption and surfactant addition could cause effects on uptake that were different from those observed at lower herbicide doses. In particular, the influence of EO content on glyphosate uptake was now much less marked in both species, especially with AM surfactants. The fundamental importance of glyphosate concentration for its uptake was further emphasised by experiments using formulations with constant a.i./surfactant weight ratios. Any increased foliar penetration resulting from inclusion of surfactants in 0·5 g litre^?-1 [¹⁴C]glyphosate formulations gave concomitant increases in the amounts of radiolabel that were translocated away from the site of application. At these low herbicide doses, translocation of absorbed [¹⁴C]glyphosate in wheat was c. twice that in field bean; surfactant addition to the formulation did not increase the proportion transported in wheat but substantially enhanced it in field bean.     

Adjuvant Effects on the Therapeutic Control of Potato Late Blight by Dimethomorph Wettable Powder Formulations

Dimethomorph is an effective Oomycete fungicide useful for the control of late blight (Phytophthora infestans, deB) on potatoes (Solanum tuberosum, L.) by preventative (prophylactic) sprays. The results of glasshouse trials using S. tuberosum plants inoculated one day prior to treatment showed that the weak to moderate curative (therapeutic) action of a wettable powder formulation of dimethomorph (WP1) could be substantially enhanced by spray tank adjuvants. A limited survey of surfactant adjuvants indicated that enhancements of performance of WP1 varied with the ethylene oxide content in two series of surfactants, C₁₂/C₁₄ alcohol ethoxylates (‘Genapol’ C series) and nonylphenol ethoxylates (‘Arkopal’ N series). Optimum enhancements were obtained with intermediate degrees of ethoxylation and ‘Genapol’ C080 was adjudged to be marginally superior to its analogues and superior to all of the ‘Arkopal’ series, as well as to a silicone ethoxylate/propoxylate (‘Silwet’ L-77), an alkylamine ethoxylate/propoxylate (‘Armoblen’ 557), and sodium sulfosuccinate (‘Aerosol’ OTB). It was also superior to an emulsifiable paraffinic/naphthenic oil (HVI 60E). Further trials established that relatively high application rates (1000–1500 g ha⁻¹) of ‘Genapol’ C080 were required for maximum enhancement and that the presence of mancozeb, as a co-fungicide, did not substantially affect the enhancement of the therapeutic performance of dimethomorph by ‘Genapol’ C080.     

DL-α-生育酚聚乙二醇琥珀酸酯类非离子表面活性剂的合成及其在农药制剂中的应用

使用DL-α-生育酚作为表面活性剂的亲油端,聚乙二醇(polyoxyethylene ether,EO)链作为亲水端,合成了非离子表面活性剂DL-α-生育酚甲氧基聚乙二醇琥珀酸酯(DL-α-tocopherol methoxypolyethylene glycol succinates),简称TPGS-X-M(X=750,1000,1500,1900,表示所使用聚乙二醇单甲醚的相对分子质量),测定了该表面活性剂的临界胶束浓度(cmc)、静态和动态表面张力,进一步将该表面活性剂用作20%乙螨唑悬浮剂中的分散剂并测试了其理化参数,与商品化分散剂FS3000进行了对比。静态表面张力测试结果表明,聚乙二醇链的长度对cmc值的影响不大;动态表面张力测试结果显示,TPGS-1000-M、TPGS-1500-M和TPGS-1900-M在1249.3 ms时的动态表面张力下降的趋势较FS3000更大,具有一定优势。性能测试结果表明,以TPGS-1500-M和TPGS-1900-M制备的20%乙螨唑悬浮剂的粒径、悬浮率、有效成分含量、分散性、热贮稳定性以及低温稳定性与以FS3000制备的悬浮剂相当。新合成的表面活性剂TPGS-1500-M和TPGS-1900-M有望作为悬浮制剂的分散剂使用。     

Effects of some nonionic polyoxyethylene surfactants on uptake of ethirimol and diclobutrazol from suspension formulations applied to wheat leaves

The influence of a number of commercial nonionic polyoxyethylene surfactants on the foliar penetration and movement of two systemic fungicides, ethirimol and diclobutrazol, was studied in outdoor-grown wheat plants at different growth stages and post-treatment temperatures in two consecutive growing seasons. Both fungicides were applied as ca 0·2 μl droplets of aqueous suspension formulations containing 0·5 g litre^?1 of ¹⁴C-labelled active ingredient; surfactants were added to these suspensions at concentrations ranging from 0·2-10 g litre^?1. To achieve optimum uptake of each fungicide the use of surfactants with different physicochemical properties was required. For diclobutrazol, a lipophilic compound, uptake of radiolabel was best with surfactants of low mean molar ethylene oxide (E) content (5-6) but it was necessary to use concentrations of ca 5 g litre^?1 to attain this. The surfactant threshold concentration for uptake enhancement of radiolabel from ethirimol formulations (< 2 g litre^?1) was much lower than that for diclobutrazol but surfactants with E contents > 10 induced the greatest amount of uptake. For both fungicides, surfactants with an aliphatic alcohol hydrophobe were generally more efficient in promoting their uptake than those with a nonylphenol moiety. The sorbitan-based surfactant ‘Tween 20’ proved to be an effective adjuvant only for the ethirimol formulation; the uptake enhancing properties of the block copolymer ‘Synperonic PE/F68’ were weak. Uptake performance could not be related to the spreading properties of the respective formulations on the wheat leaf surface or to differences in solubilisation of the two fungicides by the surfactants. Although surfactants could substantially increase the amount of acropetal transport of radiolabel from both fungicides, none of those tested specifically promoted it; a constant proportion of the radioactive dose absorbed by a treated leaf was usually exported away from the site of application. The results are discussed in the light of current theories about the mode of action of surfactants as spray adjuvants.     

In-vivo evaluation of adjuvants for more effective control of celery leaf-spot (Septoria apiicola) and powdery mildew (Erysiphe graminis) of wheat with fungicides

The effects of seven adjuvants (at 0, 0.5, 1.0 and 2.0 g litre^?1) on the efficacies of four fungicides al 0.5 g litre^?1 were studied in the laboratory for the control of leaf-spot in celery (caused by Septoria apiicola) and powdery mildew on winter wheat (caused by Erysiphe graminis). The most effective fungicides for controlling leaf-spot were: tebuconazole + triadimenol = flutriafol > mancozeb + oxadixyl > prochloraz. However, addition of adjuvant to the fungicides gave a modified pattern of effectiveness. The efficacy of flutriafol was strongly enhanced by addition of all adjuvants, but those of prochloraz and mancozeb+oxadixyl only partially so. The tested adjuvants were mineral oil + surfactant, a polymer/alkoxylated alkyl ether blend, an ethoxylated alkylphenol, an ethoxylated hexitan ester blend, an ethoxylated nonylphenol and an alkylpolysaccharide- based adjuvant mixture. However, the addition of adjuvants to tebuconazole + triadimenol had a negative effect. Of all the adjuvants tested, the nonylphenol ethoxylate and a mixture of mineral oil /surfactant and alkylpolysaccharides gave the highest efficacy with the fungicides, while the mineral oil/surfactant and the alkylpolysaccharides alone were less effective. There was a positive relationship between high concentrations of adjuvants and their effectiveness, but there were some exceptions. The most effective fungicides for control of powdery mildew in wheat were prochloraz, mancozeb + oxadixyl and tebuconazole + triadimenol. There was a linear relationship between the high efficacy of the fungicide and the concentration of adjuvants to control powdery mildew in wheat. The highest concentration of adjuvant (2-0 g litre^?1) gave the highest efficacy for the fungicides.