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1.
Reversed-phase high-pressure liquid chromatography (h. p. l. c.) and thin-layer chromatography (t. l. c.), on commercially available, reversed stationary phases, were used to determine the octan-1-ol/water partition coefficients (P) for 20 non-ionic organic chemicals, consisting mainly of known pesticides in common use. Good correlation was found between log P values and both the logarithms of the capacity factor (k′), obtained by h. p. l. c., and the Rm values derived from t. l. c. The methods were found to be applicable over a range of more than six orders of magnitude in P values. In addition, the relation is shown between the P values of organic chemicals and their solubilities in water and in octan-1-01. 相似文献
2.
Fernando Sicbaldi Gian Attilio Sacchi Marco Trevisan Attilio A. M. Del Re 《Pest management science》1997,50(2):111-119
A pressure-chamber technique was used to study the root uptake and xylem translocation of some fungicides, herbicides and an insecticide from different chemical classes in detopped soybean roots. Physiological parameters such as K+ leakage from roots, K+ concentrations in the xylem sap, and protein and ATP levels in the root cells were measured so as to evaluate any potential damage of this technique to the root system. HPLC was used to quantify the compounds in the xylem sap. The pressure-chamber technique has proved useful to study the root uptake and translocation of pesticides, does not damage the root system, and allows one to obtain appreciable volumes of xylem sap that can be analysed directly by HPLC, thus avoiding dependence on the availability of radio-labelled compounds. The concentration of each pesticide in the xylem sap showed a steady-state kinetic profile. Non-linear regression analysis was used to calculate the steady-state concentration and the time required to achieve 50% of the steady-state concentration (TSSC50). TSSC50 was well correlated with log Kow; the more lipophilic the compound the more time was required to reach the steady-state concentration. The efficiency of translocation was assessed by the transpiration stream concentration factor (TSCF) and a non-linear relationship between TSCF and log Kow was observed. The highest TSCF values were measured for those compounds with log Kow values around 3, a lipophilicity value similar to that reported earlier in an analogous experiment with detopped soybean plants but slightly higher than that reported in earlier experiments with intact barley plants. Lower TSCF values were obtained with chemicals with log Kow values below as well as above 3. © 1997 SCI. 相似文献
3.
Masahiro Takahashi Shinichi Kawamura Masakazu Miyakado Yuzuru Sanemitsu Shizuya Tanaka 《Pest management science》1993,39(3):169-177
The relationship between the hydrophobicity of certain herbicidal compounds and the bleaching pattern caused on radish cotyledons was investigated. Seed treatment with diphenylpyridones, as well as with established herbicides, produced three types of bleaching pattern according to their hydrophobicity. The less hydrophobic compounds caused complete bleaching of both cotyledons, but the compounds with more hydrophobicity caused only partial bleaching. The critical points for whole or partial bleaching were in the range of log Kow 4–5 (Kow: octanol/water partition coefficient), and these values were changed slightly with their chemical classes. Uptake of compounds into the seed coat took place rapidly; these compounds were then translocated slowly from the seed coat to the embryo, namely, radicle, abaxial surface of one cotyledon and marginal areas of both cotyledons. Application of these compounds to roots resulted in initial translocation to marginal areas of both cotyledons, with subsequent translocation to the middle area. It is believed that compounds taken up into the radicle were translocated to both cotyledons in a manner similar to that following application to roots. These effects following uptake by seeds can be used as a translaminal and lateral transport assay for bleaching herbicidal compounds in cotyledons. 相似文献
4.
The uptake by barley roots from nutrient solution and subsequent transport to shoots of two series of amine bases were measured over 6 to 72 h. The compounds were chosen to span systematically ranges of lipophilicity (assessed using 1-octanol/water partition coefficients, Kow) and pKa that would include commercial pesticide amines. In a series of six substituted phenethyl amines, strong bases with pKa∽9·5, all the compounds were strongly taken up by roots from solutions of pH 8·0; uptake declined substantially as the pH was lowered to 5·0, especially for the compounds of intermediate lipophilicity (log Kow 2 to 3). This uptake could be ascribed to three processes: (i) accumulation of the cation inside the root cells due to the negative charge on the plasmalemma, as given by the Nernst equation and important only for the polar compounds which have low permeation rates through membranes; (ii) accumulation into the vacuole by ion-trapping, which was the dominant process at high pH for all compounds and at all pH values for the compounds of intermediate lipophilicity; (iii) partitioning on to the root solids, substantial only for the most lipophilic compounds. Translocation to shoots was proportional to uptake by roots, this ratio being independent of external pH for each compound and being optimal for the compounds of intermediate lipophilicity. Such proportionality was also observed in a series of three weaker bases of intermediate lipophilicity, in which compounds of pKa 7·4 to 8·0 were also well taken up and translocated whereas the very weak base 4-ethylaniline (pKa 5·03) was much less so. Tests with quaternised pyridines confirmed that organic cations move only slowly through membranes. The observed behaviour of the amines could be modelled reasonably well assuming that transport within the plant was dominated by movement across membranes of the non-ionised species, and this appeared to be true even for the most lipophilic phenethylamine (log Kow 4·67) studied, though its long-distance movement would be as the protonated species. © 1998 Society of Chemical Industry 相似文献
5.
pKa values for a wide range of commonly used ionisable pesticides, together with the log Kow values of the most lipophilic form of each, have been measured using pH-metric techniques. Examples of acids, bases and multiprotic compounds from the major classes of herbicides, and a number of insecticides and fungicides that contain ionisable groups, are included. The pKa and log Kow values so obtained were generally in good agreement with values taken from the literature that were measured by other methods. The lower limit of log Kow that could be measured by the pH-metric method lay below the -0·97 obtained for amitrole, but the method could not be applied to glyphosate for which shake-flask measurements indicated log Kow below -3. The highest log Kow obtained in this study was 5·12 for pentachlorophenol. The pH-metric technique offers a rapid and convenient method to determine pKa and log Kow for ionisable compounds, especially when utilising an automatic titration system linked to a dedicated computer. 相似文献
6.
Ralph C Kirkwood 《Pest management science》1999,55(1):69-77
The plant cuticle is a highly complex membrane which forms the outer surface of the aerial portion of plants. The nature of the plant cuticle is reviewed with particular regard to its action as a potential barrier to the penetration of pesticide molecules; the role of the cuticular waxes is highlighted. The physicochemical properties of the cuticle influence the behaviour of spray droplets and, in turn, may affect the rate and efficiency of cuticle penetration. The permeation of active ingredients is influenced by their solubility characteristics as indicated by octanol/water (log Kow) and cuticle/water (Kcw) partition coefficients. Penetration of hydrophilic compounds (low log Kow) may be enhanced by hydration of the cuticle, while transcuticular transport of non-polar solutes (high log Kow) is increased by factors which reduce wax viscosity. The use of in-vitro models involving isolated cuticle membranes, isolated cuticle waxes, or isolated leaves has helped to focus on the activities of the cuticle in the absence of other physiological factors. Using these systems, the role of the waxes as a transport-limiting barrier has been identified and the factors influencing sorption, permeance and desorption examined. The action of surfactants, in vitro and in vivo, has been briefly addressed in regard to their role in facilitating cuticle penetration; other steps involving surfactant/solute/cuticle are complex, and synergy appears to depend on a number of factors including test species, concentration of active ingredient, surfactant type and concentration. Adjuvants may greatly influence the surface properties of the droplet, predispose the cuticle to solute transport, and enhance pesticide activity. The nature of these complex inter-relationships is discussed. © 1999 Society of Chemical Industry 相似文献
7.
Uptake and translocation of 26 chemicals (herbicides, fungicides, growth regulators, insecticides and model compounds), formulated with and without ‘Ethylan TU’ (NP8) surfactant, have been determined 24, 48 and 72 h after spraying onto leaves of maize, rape, strawberry and sugar beet. Eight of the chemicals may be classified as polar (log partition coefficient (P) < 0) and 18 as lipophilic (log P 0·8-4·6). Chemicals penetrated more readily into waxy leaves of rape and strawberry than into less-waxy sugar beet, whilst lowest rates were observed for maize. Rates of uptake varied from exceedingly low (< 2% 72 h after application) for uracil, maleic hydrazide, isoproturon and methyl phenylurea applied to maize, to rapid (>98% within 24 h of application) for acephate and triadimefon applied to strawberry leaves. The effects of NP8 on rates of chemical uptake were classified into 4 types, viz:-
- (i) low rates, with limited enhancement by NP8;
- (ii) high rates unaffected by NP8;
- (iiii) marked enhancement by NP8 within 24 h; and
- (iv) continuous enhancement by NP8 over 0-72 h.
8.
Transport of atrazine (ATR), 2,4-dinitrotoluene (DNT), and 1,2,3-trichlorobenzene (TCB) from roots to shoots via xylem of wheat and tomato seedlings was measured following a 24-h exposure of plant roots to hydroponic solutions of these organic compounds. Transport of the compounds from roots to shoots reached equilibrium within 24 h, consistent with an earlier finding. Low concentrations of TCB were detected in the final external solution and the xylem efflux of control wheat seedlings. This suggested that there was a fast foliar uptake of TCB and its downward movement via phloem of the wheat seedlings. Concentrations of DNT, ATR, and TCB in xylem effluxes of wheat and tomato increased significantly with increases of their external concentrations. The translocation stream concentration factors (TSCF), i.e., the ratios of the concentrations in xylem sap to those in external solution, of the compounds with tomato seedlings followed the order of ATR > DNT >> TCB, which was inversely correlated with the log Kow (the octanol–water partition coefficient) of the compounds. The observed xylem transports of DNT and TCB from roots to shoots with wheat seedlings were lower than those with tomato seedlings. ATR exhibited a high xylem transport with the two plant species, which resulted presumably from an atrazine–metal complex formation. 相似文献
9.
Geoffrey G. Briggs Richard H. Bromilow Avis A. Evans Mark Williams 《Pest management science》1983,14(5):492-500
Determinations were made of the distribution of two series of non-ionised chemicals, O-methylcarbamoyloximes and substituted phenylureas, in barley shoots, following uptake by the roots from solution. The concentrations in basal and central shoot sections became constant after 24 to 48 h for all but the most lipophilic chemical studied, and were then greatest for the more lipophilic chemicals. Amounts in the leaves generally increased up to 72 or 96 h, when degradation balanced translocation. The accumulation of chemical in the lower section of shoots can be ascribed to a partitioning process similar to that in roots, the chemical being partitioned between the shoot and the xylem transpiration stream; this uptake could be estimated from the octan-1-01/water distribution coefficients, and was predicted to be greatest for compounds for which log Kow=4. 5. 相似文献
10.
The driving force for foliar penetration is the product of the partition coefficient (K) between the cuticle and the formulation residue, and the concentration of the active ingredient in the spray residue. Ethylene glycols and polyethylene glycols (PEGs) are often contained in commercial formulations, because they are good solvents and not toxic. Since they are humectants, the water content of the formulation residue varies with humidity of the air. At 25°C and 65% relative humidity PEG 400 contains about 50% water. The partition coefficients for the lipophilic herbicide, bifenox, increased with increasing water content of the ethylene glycols and PEGs, such that log K was a linear function of the mass fraction of water or PEG. The K value was about 0·5 for the system cuticle/pure PEG and 27500 for the system cuticle/water. When PEG contained 50% water, K was only 110. Partition coefficients of bifenox between cuticle and ‘Tween’ 80 depended also on humidity, having values of 0·75 in cuticle/pure ‘Tween’ 80 and 29·1 when ‘Tween’ 80 contained 50% water. With 1-naphthylacetic acid (NAA), which is a weak acid, partition coefficients also depended on water content of PEG 400, but a maximum curve was obtained. The maximum partition coefficient (211) was observed with a mixture of 30% PEG 400 and 70% water, which corresponded to a humidity of 88%. We suggest that this is due to an effect of PEG 400 on the ionisation of NAA. Our data demonstrate that partition coefficients are affected by humidity, because solubilities of lipophilic compounds and weak acids in PEG/water mixtures vary greatly with the water content. This in turn affects driving forces, mainly by the effect of humidity on partition coefficient. With non-ionisable lipophilic compounds, partition coefficients, driving forces and rates of foliar uptake therefore increase with increasing humidity. © 1998 SCI 相似文献
11.
Eight new sterol biosynthesis-inhibiting fungicides, structurally related to penconazole and having vapour pressures up to 118 mPa, were synthesised. Their toxicities to the cereal take-all fungus, Gaeumannomyces graminis var. tritici, on agar were measured; intrinsic activities were measured after incorporating the compounds into the agar and vapour activities were measured after their evaporation from glass and from moist soil. Vapour activity following evaporation from soil was shown to be a function of both the intrinsic activity of the compound and its partition coefficient between the air and moist soil (Kas). The latter is itself a function of vapour pressure, 1-octanol/water partition coefficient (Kow) and the soil type. The compound most active as vapour from soil in the in-vitro test, 1-(pyridin-3-yl)-2-(4-flurorophenyl)pentane, was ineffective against take-all in wheat in a pot test in which the inoculated soil was treated unevenly, providing further evidence that the redistribution of fungicides in moist soil occurs predominantly via the water phase rather than the vapour phase. 相似文献
12.
The effects of polydisperse ethoxylated fatty alcohol (EFA) surfactants on the penetration of six organic compounds varying in size (molar volumes, 107–282 cm3 mol-1) and lipophilicity (log Kow 0·8–6·5) were investigated using astomatous isolated cuticular membranes (CM) of Citrus and pear leaves. Mobilities of model compounds in CM were measured by unilateral desorption from the outer surface (UDOS). Rate constants (k*) obtained in these experiments are directly proportional to diffusion coefficients and, in the absence of EFA, k* values decreased by a factor of 52 when molar volumes increased only 2·64-fold. Under UDOS conditions using micellar surfactant solutions as desorption media, surfactants are sorbed in the CM and the volume fractions sorbed were found to decrease from approximately 0·062 to 0·018 when the average number of ethoxy groups (nE) increased from 5 to 17. In the presence of the EFA surfactants in the CM, solute mobilities increased markedly though this effect diminished with increasing nE. Surfactants with nE=17 affected solute mobilities only marginally. Surfactant effects on solute mobility increased with the size of the solutes leading to almost identical mobilities of the model compounds. With the current range of our model compounds, lipophilicity increased with increasing molar volumes, though evidence is presented showing that the mobilities of solutes depend on their molar volumes while lipophilicity has no effect. Effects of micellar aqueous solutions of polydisperse surfactants on solute mobilities followed the pattern observed with monodisperse ones. © 1997 SCI 相似文献
13.
Lignin, an important component of plant tissues, adsorbed five systemic fungicides and one herbicide (carbendazim, triadimefon, nuarimol, triarimol, fenarimol and fluometuron) more strongly than bovine serum albumin, cellulose, ethylcellulose or sodium polygalacturonate. Significant correlations were found between the extent of the adsorption of the pesticides on the lignins extracted from three different plant species, and the log Poet (Poet is the octan-1-ol/water partition coefficient) of the compounds. The more lipophilic fungicides triarimol and fenarimol (log Poet about 2.6) were adsorbed to the greatest extent. Fluometuron, triadimefon and nuarimol (log Poet about 2.0) were moderately adsorbed, whereas carbendazim with the lowest log Poet (1.34 at pH 5.0), was adsorbed more than expected from its Poet value. The anomaly of carbendazim is discussed; it is ascribed to it's partial protonation at pH 5.0, whereas the other pesticides were non-ionised. 相似文献
14.
Isao Tada Minoru Motoki Nobuyoshi Takahashi Tetsuji Miyata Tomoko Takechi Toshiro Uchida Yasushi Takagi 《Pest management science》1996,48(2):165-173
A series of novel 4,5-dihydropyrazole-5-thiones (DHPs) was synthesised by treating the corresponding dihydropyrazolones with ‘Lawesson’s reagent and evaluated for miticidal activity against two-spotted spider mites (Tetranychus urticae Koch). Of these, 3-(4-chlorophenyl)-4,4-dimethyl-1-phenyl-4,5-dihydropyrazole-5-thione, 3-(4-chlorophenyl)-4-ethyl-4-methyl-1-phenyl-4,5-dihydropyrazole-5-thione, 3-(4-chlorophenyl)-1-phenyl-4,5-dihydropyrazole-5-thione-4-spirocyclopentane and 4,4-dimethyl-1-phenyl-3-(4-trifluoromethyl-phenyl)-4,5-dihydropyrazole-5-thione were highly active (pEC50>4·0) and were more effective than the miticide dicofol (pEC50=3·879), which has traditionally been used for the control of phytophagous mites. Structure–activity relationship (SAR) studies were performed on each position of the pyrazole ring of DHPs. The results indicated that the unsubstituted phenyl, 4-substituted phenyl and thioxo groups on the 1-, 3- and 5-positions of DHPs respectively were required for activity. Quantitative SAR studies using physicochemical parameters of substituents and the capacity factor k′ as a hydrophobicity index suggested that: (a) the activities of all types of DHPs examined were mainly dominated by hydrophobicity, (b) the bulkiness of 4-substituents of the 3-phenyl ring favoured the activity and (c) the log k′ optimum for all DHPs was 1·675, equivalent to a log Pow value of c. 5·0. 相似文献
15.
David Stock Peter J. Holloway B. Terence Grayson Paul Whitehouse 《Pest management science》1993,37(3):233-245
Composition-concentration relationships between a series of C13/C14 polyoxyethylene primary alcohol (AE) surfactants and the foliar uptake enhancement of five model neutral organic compounds were examined in factorially designed experiments on wheat (Triticum aestivum L.) and field bean (Vicia faba L.) plants grown under controlled environment conditions. Model compounds were applied to leaves as c.0.2-μl droplets of 0.5 g litre?1 solutions in aqueous acetone in the absence or presence of surfactants at 0.2, 1 and 5g litre?1. Uptake of the highly water-soluble compound, methylglucose (log octanol-water partition coefficient (P) = - 3.0) was best enhanced by surfactants with high E (ethylene oxide) contents (AE15, AE20), whereas those of the lipophilic compounds, WL110547 (log P = 3.5) and permethrin (log P = 6.5), were increased more by surfactants of lower E contents, especially AE6. However, there was little difference between AE6, AE11, AE15 and AE20 in their ability to promote uptake of the two model compounds of intermediate polarity, phenylurea (log P = 0.8) and cyanazine (log P = 2.1). Absolute amounts of compound uptake were also influenced strongly by both surfactant concentration and plant species. Greatest amounts of uptake enhancement were often observed at high surfactant concentration (5 g litre?1) and on the waxy wheat leaves compared with the less waxy field bean leaves. The latter needed higher surfactant thresholds to produce significant improvements in uptake. Data from our experiments were used to construct a simple response surface model relating uptake enhancement to the E content of the surfactant added and to the physicochemical properties of the compound to be taken up. Qualitative predictions from this model might be useful in rationalising the design of agrochemical formulations. 相似文献
16.
Satoshi Gotoda Nobuyoshi Takahashi Hirofumi Nakagawa Mitsuyuki Murakami Tomoko Takechi Tomozo Komura Toshiro Uchida Yasushi Takagi 《Pest management science》1998,52(4):309-320
A series of novel 6-(1,2,4-triazol-4-yl) chromone and -1-thiochromone (benzo[b]thiazin-4-one) derivatives was obtained by cyclisation via thiosemicarbazides which were prepared by reaction of hydrazines and the corresponding isothiocyanates. Their fungicidal activity was evaluated against the rice blast fungus Pyricularia oryzae. Of this series, 2,5,8-trimethyl-6-(1-propyl-5-thioxo-3-trifluoromethyl-1,2,4-triazol-4-yl) chromone, 6-(1-butyl-5-thioxo-3-trifluoromethyl-1,2,4-triazol-4-yl)-2,5,8-trimethylchromone, 6-(1-hexyl-3-methyl-5-thioxo-1,2,4-triazol-4-yl)-2,5,8-trimethylchromone and 6-(1-allyl-5-thioxo-3-trifluoromethyl-1,2,4-triazol-4-yl)-2,5,8-trimethylchromone were highly active (pEC50>6·0). Structure–activity relationship studies using the capacity factor k′ as a hydrophobicity index suggested that the log k′ optimum for 2,5,8-trimethyl-chromone and -1-thiochromone derivatives was around 1·0, equivalent to a log Pow value of c. 4·4. © 1998 SCI 相似文献
17.
18.
Dhirendra Singh 《Pest management science》2000,56(2):195-201
The adsorption of carbofuran on soils from water‐methanol mixtures has been evaluated by batch shake testing. Two uncontaminated soils having different physicochemical properties were used in these experiments. The volume fraction of methanol in the liquid phase (fs) was varied from 0.25 to 1.0. Higher adsorption of carbofuran was observed in medium black (silt loam) soil than in alluvial (sandy loam) soil; calculated values of the Freundlich constant (Km) and distribution coefficient (Kd) showed that adsorption of carbofuran in both soils decreased with increase in fS values. The decreased carbofuran adsorption in methanol–water mixtures meant a greater potential of ground‐water contamination through leaching from potential sites. The data have been used to evaluate the co‐solvent theory for describing adsorption of carbofuran in methanol–water mixtures. The aqueous phase partition coefficient Kdw (mol g−1) normalized with respect to foc and the aqueous phase adsorption constant Kw for carbofuran were evaluated by extrapolating to fS = 0. © 2000 Society of Chemical Industry 相似文献
19.
Toxicity and repellency effects of several pure compounds (of plant origin) against the confused flour beetle (Tribolium confusum) were investigated in a filter paper test. The compounds were α-pinen, β-pinen, 4-allyl-anisol, camphor, 1,8-cineol, eugenol,
linalool, menthol, piperin, terpineol, thymol and zimtaldehyde. Five compounds (4-allyl-anisol, linalood, terpineol, thymol
and zimtaldehyde) caused enough mortality of this insect to allow the determination of LD50 and LD95 values. Zimtaldehyde and 4-allyl-anisol showed the strongest toxicity effects with LD50 values of 0.04–0.05 μl/cm2 within an exposure period of 24 h. When the isolated fumigant effects were tested by separating the insects from the filter
paper, the toxicity of zimtaldehyde (LD50=0.29 μl/cm2) was much lower than that of 4-allyl-anisol (LD50=0.10μl/cm2). 相似文献
20.
Toxicity and repellency effects of several pure compounds (of plant origin) against the confused flour beetle (Tribolium confusum) were investigated in a filter paper test. The compounds were α-pinen, β-pinen, 4-allyl-anisol, camphor, 1,8-cineol, eugenol, linalool, menthol, piperin, terpineol, thymol and zimtaldehyde. Five compounds (4-allyl-anisol, linalood, terpineol, thymol and zimtaldehyde) caused enough mortality of this insect to allow the determination of LD50 and LD95 values. Zimtaldehyde and 4-allyl-anisol showed the strongest toxicity effects with LD50 values of 0.04–0.05 μl/cm2 within an exposure period of 24 h. When the isolated fumigant effects were tested by separating the insects from the filter paper, the toxicity of zimtaldehyde (LD50=0.29 μl/cm2) was much lower than that of 4-allyl-anisol (LD50=0.10μl/cm2). 相似文献