Physico-chemical factors determining the phloem translocation of benzoic acids

A series of ¹⁴C-labelled benzoic acids, chosen to permit assessment of the role of pK_a and lipophilicity in determining movement in plants of these herbicide analogues, was synthesised and their phloem translocation investigated. Following application of substituted benzoic acids to castor bean, Ricinus communis L., by injection into the petioles, the compounds of intermediate lipophilicity (2-fluoro-, 4-chloro- and 3,4-dichlorobenzoic acids) gave highest concentrations in phloem exudates; 4-methyl-2,3,5,6-tetrafluoro- and pentafluorobenzoic acids were less well translocated, perhaps because their pK_a values are much less than those of the other benzoic acids studied. The polar 4-ureidobenzoic acid and the lipophilic 3-(4-methylphenoxy)benzoic acid were much less efficiently translocated in phloem. These results are similar to those previously obtained for phenoxyacetic acids, and provide further support for the role of ionisation in the accumulation and retention of chemicals in phloem sieve tubes.     

Relationships between lipophilicity and the distribution of non-ionised chemicals in barley shoots following uptake by the roots

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 K_ow=4. 5.     

Physicochemical factors affecting the uptake by roots and translocation to shoots of amine bases in barley

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, K_ow) 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 K_ow 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 K_ow 4·67) studied, though its long-distance movement would be as the protonated species. © 1998 Society of Chemical Industry     

Relationships between lipophilicity and root uptake and translocation of non-ionised chemicals by barley

The uptake by roots from solution, and subsequent translocation to shoots in barley, of two series of non-ionised chemicals, O-methylcarbamoyloximes and substituted phenylureas, were measured, Uptake of the chemicals by roots was greater the more lipophilic the chemical, and fell to a lower limiting value for polar chemicals. Translocation to the shoots was a passive process, and was most efficient for compounds of intermediate polarity. Both processes had reached equilibrium within 24h of treatment. The reported behaviour of many pesticides in various plant species agrees with the derived relationships, but the detailed mechanisms of these processes are unknown.     

Uptake by roots and translocation to shoots of two morpholine fungicides in barley

Despite being lipophilic, morpholine fungicides are systemic in plants. Such transport may be explicable by their protonation (pKa∽7·5) at the pH of plant compartments to yield the more polar cation. This behaviour might be a useful attribute to be incorporated into other classes of lipophilic pesticides. To understand quantitatively the behaviour of the morpholine fungicides, the uptake by roots and transport to shoots in barley of two such ¹⁴C-labelled compounds, dodemorph and tridemorph, were investigated using bathing solutions of differing pH. At pH 5, uptake and transport were small, but increased by approximately two orders of magnitude at pH 8. Tridemorph, the more lipophilic of the two compounds, was highly accumulated by roots at pH 8 and moderately translocated to shoots. In contrast, dodemorph was translocated to shoots at pH 8 with remarkable efficiency, moving into the xylem across the endodermis at 23 times the efficiency of water, though accumulation in roots was less than that of tridemorph. Behaviour at 24 h was largely similar to that at 48 h for both compounds, indicating that uptake and translocation are equilibrium processes maintained over time. Transport to shoots for each compound was directly proportional to the concentrations accumulated in the roots, except at low pH where partitioning into root solids became proportionately more important with such material not being directly available for transport to the xylem across the endodermis. Uptake and transport of these basic fungicides are explained in terms of their partitioning and of their accumulation in acidic plant compartments by ion trapping as the protonated form; this behaviour is discussed in relation to the pKa and lipophilicity of these compounds. © 1998 Society of Chemical Industry     

Potassium uptake in atrazine-treated roots of sensitive and resistan plants

The action of atrazine and its biodegradation products on the membrane transport of potassium in roots was evaluated in both sensitive and resistant plants. Excised roots of maize and oat showed inhibition of potassium uptake efficiency in the presence of 1.4 × 10^?4M atrazine and 1.4 × 10^?4M deethylated atrazine. Other biodegradation products such as 2-chloro-4-amino-6-ethylamino-1,3,5-triazine,2-chloro-4,6-,bisamino-1,3,5-triazine, and 2-chloro-4-amino-1,3,5-triazine showed no inhibitory effect on the K⁺ uptake capacity. Two maize hybrids showing different uptake efficiency were inhibited differently by atrazine. We suggest that atrazine and deethylated atrazine inhibited the K⁺ transport interacting directly with the plant cell membranes without discerning between resistant and sensitive plants.     

Uptake and translocation of non-ionised pesticides in the emergent aquatic plant parrot feather Myriophyllum aquaticum

The uptake of four (14)C-labelled non-ionised compounds, the methyl carbamoyloxime insecticide/nematicide oxamyl and three model phenylureas, from solution by rooted stems of the aquatic plant parrot feather [Myriophyllum aquaticum (Vell.) Verdc], together with translocation to the emergent shoots, was measured over periods of 24 and 48 h. Uptake into the submerged tissues of roots and stem base could be ascribed to two processes: movement into the aqueous phase of cells and then partitioning onto the plant solids. This latter process was related to lipophilicity (as measured by the l-octanol/water partition coefficient, K(ow)) and gave rise to high uptake rates of the most lipophilic compounds. Translocation to shoots was passive and was optimal at log K(ow) approximately 1.8, at which the efficiency of translocation of compound was about 40% of that of water. This optimum log K(ow) was identical to that observed previously in barley, although the translocation efficiency was somewhat less in parrot feather. Solvation parameters were applied to model uptake and translocation of a set of ten compounds by barley with the particular objective of understanding why translocation efficiency is lower at log K(ow) > 1.8.     

Modeling root absorption and translocation of 5-substituted analogs of the imidazolinone herbicide,imazapyr

Quantitative structure-activity relationships (QSAR) were developed between the physicochemical parameters of the 5-substituent of a series of analogs of the imidazolinone herbicide, imazapyr, and root absorption, translocation, inhibition of acetohydroxyacid synthase (AHAS), and herbicidal activity of the analogs. An optimum substituent lipophilicity (π = 1.85–2–3) for root absorption was identified for corn (Zea mays L.) and sunflower (Helianthus annuus L.). Translocation from roots to shoots was greatest for those analogs having either highly nonpolar or highly polar 5-substituents, indicating that both symplastic and apopiastic mechanisms may be functioning. In addition, translocation from roots was positively correlated with electron-withdrawing parameters of the 5-substituent, and a possible mechanism governing this relationship is discussed. Modeling in vitro AHAS inhibition was not successful, but models were developed for herbicidal activity as measured in an Arabidopsis thaliana (L.) Hevnh. bioassay. The whole-plant models described an optimum substituent lipophilicity (π = 0 71) which probably reflected the influence of this parameter on the component processes of absorption and translocation. Whole-plant activity was also greater for analogs having electron-donating 5-substituents; this result suggests that electron donation may be important for metabolism, or more likely, for AHAS inhibition.     

Relationship between safening activity of dymron and fenclorim to pretilachlor and glutathione S-transferase activity in rice

Dymron [1‐(α,α‐dimethybenzyl)‐3‐(p‐tolyl)urea] and fenclorim (4,6‐dichloro‐2‐phenylpyrimidine) were found to exhibit a safening activity on the growth of rice (Oryza sativa L.) seedlings against pretilachlor [2‐chloro‐2′,6′diethyl‐N‐(2‐propoxyethyl)acetanilide] injury. By pretilachlor treatment at 10^–6 and 10^–5 mol L^–1, the elongation of the third leaves of rice seedlings was reduced by approximately 20 and 40%, and that of the fourth leaves was reduced by approximately 40 and 80%, respectively. Upon the treatment of dymron at 3 × 10^–6 and 10^–5 mol L^–1 in combination with pretilachlor, the growth inhibition was half alleviated in the third leaves, and the length of the fourth leaves was almost recovered from 10^–6 mol L^‐1 pretilachlor injury, and was 20–25% recovered from 10^–5 mol L^–1 pretilachlor injury. Upon the treatment of fenclorim at 3 × 10^–6 and 10^–5 mol L^–1 in combination with pretilachlor, the growth inhibition of rice seedlings was almost alleviated in both the third and the fourth leaves. This result indicated that dymron and fenclorim showed almost the same safening effect on the fourth leaf growth against 10^–6 mol L^‐1 pretilachlor injury, although fenclorim showed higher effects at higher concentrations of pretilachlor. Glutathione S‐transferase (GST) activities in rice seedlings were investigated after being treated with a herbicide and safener. By pretilachlor treatment at 10^–6 and 10^–5 mol L^–1, the GST activity was approximately 32 and 72% increased in roots, respectively, and a little increased (7–13%) in shoots of two‐leaf‐stage rice seedlings. By dymron treatment at 3 × 10^–6?10^–5 mol L^–1, the GST activity was 2–30% increased in roots, but was not increased in shoots. By their combination treatment, the GST activity was almost the same or less than that by treatment with pretilachlor alone. In contrast, by fenclorim treatment alone, the GST activity was 43–52 and 33–45% increased in roots and shoots of rice seedlings, respectively. By the combination treatment of pretilachlor and fenclorim, the GST activity was increased 73–126% in shoots and 101–139% in roots, and was much more increased in both shoots and roots compared with treatment of pretilachlor or fenclorim alone. It was found that dymron showed less effect in increasing the GST activity than fenclorim. It is also suggested that dymron did not increase the GST activity in shoots but did increase it slightly in roots, and showed almost no effect on GST increase by pretilachlor in shoots, or rather reduced the increase in roots. From the above results, fenclorim and dymron may have different mechanisms of safening effects on the protection of rice seedlings against pretilachlor injury.     

Root Uptake and Xylem Translocation of Pesticides from Different Chemical Classes

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 K_ow; 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 K_ow was observed. The highest TSCF values were measured for those compounds with log K_ow 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 K_ow values below as well as above 3. © 1997 SCI.     

Uptake and translocation of [14C]asulam and [14C]bromacil by roots of maize and bean plants

The uptake and translocation of ¹⁴C-ring-labeled asulam (methylsulfanilcarbamate) and bromacil (5-bromo-3-sec-butyl-6-methyluracil), were compared after root application to maize (Zea mays L.) and bean (Phaseolus vulgaris L.). Autoradiographs showed the distribution of bromacil throughout these and other plant species, and the retention of asulam in the roots. The recovery of both compounds in quantitative radioassays was between 90 and 100%. The absorption of bromacil and asulam was rather similar. Absorption of bromacil increased up to 20% of the applied dose in bean plants after 2 days of exposure, and up to 11% in maize plants after 4 days. Absorption of asulam in bean plants was 22% of the applied dose after 2 days, and 8% in maize plants after 4 days. The pattern of distribution of bromacil and asulam was completely different. After 4 h of exposure of the roots about half of the absorbed bromacil had accumulated in the shoots, while two-thirds or more was translocated to the shoots after exposure periods of 1 to 4 days. Not more than one-eighth of the absorbed asulam was found in the shoots. In consequence, the bromacil content in the transpiration stream relative to that in the ambient solution was much higher than that of asulam. The leakage of asulam from bean and maize roots into herbicide-free nutrient solution was lower than that of bromacil. The reasons for these differences are not yet clear. There was only some metabolism of asulam in maize, but not in bean plants. No metabolites of bromacil were detected in the two plant species.     

The metabolism in the rat of the herbicidally active isomer (R)- flamprop-methyl in comparison with the racemic form

A single dose (4 mg kg^?1) of ¹⁴ C-labelled (R)-flamprop-methyl to rat was rapidly metabolised and 90% of the dose was eliminated in urine and faeces within 48 h. Four days after dosing, tissue residues were 0–1 μg equivalents g^?1 tissue or much less, with the exception of kidney (0–22 μg g^?1). There was a statistically significant sex difference in the routes of elimination; this may be attributed to differences in the biliary elimination of the major metabolite, flamprop acid, or its glucuronide conjugate. The fate of racemic flamprop-methyl was very similar to that of the (R)-isomer. The major metabolic routes were hydrolysis of the esters to the corresponding acids, hydroxylation of the benzoyl aromatic rings and conjugation. The flamprop acid derived from the (R)-flamprop-methyl was found to be partially converted to the (S)-form (R:S ratio, 87:13). This reaction is discussed in the context of other such biological racemisations recently reported.     

Effect of CGA 123407 as a safener for pretilachlor in rice (Oryza sativa L.). Recordings of elongation rates of single rice leaves

The elongation rates of single attached leaves of rice (Oryza saliva L.) were recorded. The effect of pretilachlor on the elongation rates and the safening effect of CGA 123407 [4, 6-dichloro-2-phenyl-pyrimidine] were evaluated. Both chemicals were applied to the roots in a nutrient solution. Pretilachlor reduced leaf elongation in concentrations as low as 300 μg^?1 (9–6 × 10^?7 M) but. for combination trials with the safener, 3 mg 1^?1 (9–6 × 10^?6 M) was used. in combination with pretilachlor the safener prevented damage in very low concentrations. The ratio of pretilachlor to safener, 30:1, was sufficient when both chemicals were given to roots in nutrient solution, although for field work the ratio of 3:1 is recommended. The safener alone did not influence the elongation rate of rice leaves in the concentrations used. When pretilachlor was given to the roots and CGA 123407 to the shoot, some delay in the herbicidal action was recorded but even with high concentrations of the safener no continuous safening effect was achieved. CGA 123407 was also effective when given previous to the herbicide. This proved true even with a 2-day interval between safener uptake and application of the herbicide. When pretilachlor was given first, the safener effected recovery to various degrees when given 1–4 days after the herbicide application. When pretilachlor was given for a limited period of time only (1–3 days) and was subsequently removed from the nutrient solution, recovery of the plant occurred. It is speculated that the safener either helps this recovery or else competitively prevents the herbicide from occupying the sites of action or from keeping them occupied for a long period of time.     

Uptake and fate of triticonazole applied as seed treatment to spring wheat (Triticum aestivum L.)

Following seed treatment of wheat (Triticum aestivum L.) with ¹⁴C-labelled triticonazole at a dose of 1·8 g kg^-1 seed, the uptake of radioactivity by shoots and roots was investigated from the two- to three-leaf stage up to the beginning of the booting phase, 80 days after sowing. Triticonazole equivalents taken up by wheat plants reached 5·7% and 14·6% of the applied dose in the shoots and the roots, respectively. Between the two- to three-leaf stage and the beginning of the booting phase, the concentration of triticonazole equivalents in the shoots decreased from 2·5 to 0·15 μg g^-1 fresh weight. This was attributed to uptake of triticonazole by roots not keeping pace with shoot growth and increased retention in the roots of triticonazole taken up. The main factor limiting the uptake of triticonazole by the roots may be the rapid growth of the uptake-active apical root parts out of the dressing zone which had formed in the soil. Distribution of triticonazole equivalents taken up by the main shoot showed a decreasing concentration gradient from the oldest to the youngest leaf. An increase in the seed treatment dose was investigated as a way to increase the concentration of triticonazole in the shoots, but its influence remained limited. © 1998 SCI     

Uptake of chemicals from foliar deposits: Effects of plant species and molecular structure

The uptake from foliar deposits of 10 ¹⁴C-labelled compounds into each of 10 species of field-grown plants was measured 26 h after deposition by combustion of leaf tissue after removal of surface deposits. The compounds, which included eight pesticides, covered a wide range of lipophilicity and each was formulated in the same way; they were applied as droplets with a microsyringe. Uptake varied greatly between the species. All compounds were taken up well into maize and Xanthium pennsylvanicum, whereas relatively little entered the leaves of apple or orange. Uptake into the six other species varied according to the compound. Amongst the eight non-polar compounds, no relationship between the rate of uptake and molecular size was discerned, and only in X. pennsylvanicum was uptake related to the partition coefficient and water solubility. Considering all the compounds, weak relationships were observed between molecular cross-sectional area and uptake into four species. The range of the uptake rates (×130) was small compared with those of octan-1-ol-water partition coefficients (×10¹⁰) and water solublities (×10⁷) shown by the 10 compounds. Possible reasons for the absence of correlations between the uptake and the molecular properties considered are discussed. The results are consistent with either separate routes of cuticular entry for non-polar and polar compounds, or a common route for both types of compound. The generally poor uptake by apple and orange leaves, which may be related to their thick cuticles, highlights the need to develop special formulations to optimise uptake into these species.     

Phloem translocation of non-ionised chemicals in Ricinus communis

Techniques using R. communis were modified to enable the movement of chemicals in phloem and the factors controlling their distribution in the plant to be described quantitatively. The non-ionised chemicals tested, aminotriazole, O-methylcarbamoyloximes (including aldoxycarb and oxamyl) and phenylureas, spanning a range of lipophilicity of log K_OW= ?0.87 to +2.27, all freely entered the phloem. However, only the more polar compounds were retained sufficiently in the phloem to be transported over long distances, indicating that polar compounds cross cell membranes more slowly than compounds of intermediate lipophilicity; these findings substantiate the ‘intermediate permeability hypothesis’ of phloem translocation of xenobiotics. However, the amount of chemical reaching or retained in the sink tissues, especially in the root, was small even for the chemicals that were translocated best in the phloem.     

Uptake, translocation and phytotoxicity of root-absorbed haloxyfop in soybean, Festuca rubra L. and Festuca arundinacea Schreb

The concentrations of haloxyfop in nutrient solution required to reduce the total plant dry weight of soybean (Glycine max L. Merr. ‘Evans’), red fescue (Festuca rubra L. ‘Pennlawn’), and tall fescue (Festuca arundinacea Schreb. ‘Houndog’) by 50% (GR₅₀) were determined. The GR₅₀) values for soybean, red fescue and tall fescue were 76 μM, 3μM and 0.4 μM, respectively. The reduction in growth in roots and shoots of soybean was similar. In contrast, the relative reduction in root tissue weight was greater than that for foliar tissue in both grass species. The amount of ¹⁴C-haloxyfop in soybean roots or shoots was higher than in red fescue or tall fescue. Red fescue accumulated less haloxyfop in the foliage than in the roots. On the other hand, similar amounts of ¹⁴C-haloxyfop accumulated in both organs in both soybean and tall fescue. ¹⁴C-haloxyfop appeared to be actively absorbed by the roots of all species. Soybean absorbed more nutrient solution, but utilized it less on a per gram dry matter produced basis than the grass species. Differences in the uptake and translocation of haloxyfop by roots do not account for differences in tolerance between species. However, a higher level of retention of haloxyfop in the roots of red fescue than in tall fescue may provide the former with an additional selectivity advantage under conditions where there is significant root exposure to the herbicide.     

几种有机硅助剂对草甘膦在单子叶植物体内吸收、转移和分布的影响

采用14C-草甘膦同位素标记法研究了4种有机硅助剂Silwet L-77、Silwet 800 、Freeway 和Boost 在体积分数0.1%用量下对草甘膦在黑麦草( Lolium perenne L. cv. Grasslands Greenstone)体内吸收、转移和分布的影响。结果表明:与单用草甘膦相比，4 种助剂的加入显著地降低了草甘膦在黑麦草体内的吸收和转移量，助剂之间无显著性差异。 处理后24和72 h测定，草甘膦主要分布在幼嫩组织中，其次是根部，在老叶片中的转移量最 少。无论转移量高低，草甘膦在植物体内的分布总是表现为地上部的比例高于地下部。有机 硅助剂对草甘膦在各组织中的分布比例没有影响。     

Uptake,distribution and metabolic fate of 3H-triforine in plants. II. Long-term experiments

Uptake of ³H-triforine by tomato and barley seedlings from soil with a high organic matter content was much less efficient than from aqueous suspensions, even though the period of exposure was much longer—at least 1 week (“long-term treatment”) vs 1 day (“short-term treatment”). After transplanting to fresh soil, part of the label in the roots was lost probably by desorption. Distribution of label in tomato shoots was as irregular as after short-term treatment; label was virtually confined to the leaves which expanded before about 14 days after cessation of the treatment. In shoots of barley seedlings which were pretreated in an aqueous suspension of ³H-triforine for 1 day before being subjected to a long-term soil treatment, almost all radioactivity present could be ascribed to uptake during the pretreatment phase. The distribution pattern strongly resembled that obtained after short-term treatment, hardly any label being found in leaves which unfolded after the pretreatment phase. Rates of conversion of ³H-triforine in barley shoots depended to some extent on whether or not seedlings were transplanted to fresh soil after 1 week.     

Mechanism of cellular absorption of imidazolinones in soybean (Glycine max) leaf discs

The mechanism of uptake of imazapyr, imazethapyr, and imazaquin into soybean leaf discs was determined. Uptake into the leaf discs was linear with respect to external concentration from 10^?8 to 10^?3 M. Metabolic inhibitors and uncouplers (DNP, FCCP, CCCP, NaN₃, NaCN, DCMU) decreased uptake 58 to 85 %. Uptake was also sensitive to temperature, with maximum uptake occurring at 23°C. The Q₁₀ for uptake between 13 and 23°C was 1-7. The uptake of all 3 imidazolinones was sensitive to the pH of the uptake solution. Maximum uptake occurred at pH 4. However, there were differences in the rate of uptake among the three herbicides. Imazaquin was absorbed the most rapidly followed by imazethapyr and then imazapyr. These differences in uptake reflected the differences in the lipophilicity of the chemicals at pH 4 and 7. The apparent K_ow of imazaquin, imazethapyr and imazapyr at pH 4 was 7-7, 1-4, and 0-1, respectively, and at pH 7 was 0-04, 0-02, and 0-004, respectively. Based on these results the mechanism of uptake is probably best explained by ion trapping.