首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 31 毫秒
1.
Metabolism of [phenyl-14C] and [(2,5) pyrrolidine-14C] cisanilide was investigated in vitro with microsomal preparations from rat liver. Microsomal activity was associated with a mixed-function oxidase system that required O2 and NADPH and was inhibited by CO. Two major ether-soluble metabolites were isolated. They were identified as primary oxidation products: 2-hydroxy-2,5-dimethyl-1-pyrrolidinecarboxanilide (A) and 4′-hydroxy-2,5-dimethyl-1-pyrrolidinecarboxanilide (B). Minor ether-soluble metabolites were also isolated. Precursor product studies and qualitative thin layer chromatography analysis of [pyrrolidine-14C] and methylated [phenyl-14C] hydrolysis products suggested that these metabolites were secondary oxidation products formed from metabolites A or B. One of these metabolites appeared to be the dihydroxy product 2,4′-dihydroxy-2,5-dimethyl-1-pyrrolidinecarboxanilide. Crude microsomal preparations (postmitochondrial supernatant fractions) also formed small quantities (<10%) of polar metabolites. Enzyme hydrolysis with β-glucuronidase (Escherichia coli) indicated that approximately 50% of these metabolites were glucuronides. Similarities and differences in cisanilide oxidation in vivo in plants and in vitro with rat liver microsomal preparations were discussed.  相似文献   

2.
The degradation of the herbicide diclofop-methyl, ( ± )-methyl 2-[4-(2,4-dichloro-phenoxy)phenoxy]propionate, was investigated in two agricultural soils under aerobic and anaerobic conditions. Using two differently labelled forms of [14C]-diclofop-methyl the qualitative as well as the quantitative formation of extractable metabolites was followed for 64 days. The mineralisation of the uniformly labelled aromatic rings was pursued by monitoring the 14CO2 generated for 25 weeks. As a first step of the degradation a very rapid hydrolysis of the ester bond was detected under all conditions. Diclofop, the corresponding substituted propionic acid formed, was extensively degraded under aerobic conditions, the final product being 14CO2. As an intermediate, a compound later identified by GLC/MS to be 4-(2,4-dichlorophenoxy)phenol, was found in the extracts. Furthermore, traces of six other unknown metabolites were detected. Under anaerobic conditions the degradation proceeded to a small extent. At most 3% of the applied radioactivity was accounted for by the degradation product 4-(2,4-dichlorophenoxy)phenol. No other metabolite, including 14CO2, was observed, implying lack of any further degradation.  相似文献   

3.
Root-treated soybean plants absorb, translocate, and metabolize isopropyl carbanilatephenyl-14C (propham-14C). After a 3-day treatment period and removal of the exogenous 14C treating solution, only small concentrations of 14C-labeled materials were found in newly emerging tissues. A measurable concentration of radiocarbon was found in the seed pods, but the fruit tissues were shown to be free of any dectable 14C-labeling. Three days after removal of the exogenous propham-14C, the parent herbicide was completely metabolized by all tissues. Polar products and nonextractable residues were found in roots, stems, and leaves after a 3-day treatment period. The polar metabolites were not translocated once they were formed in either the roots or shoots.Conjugated polar metabolites were isolated, partially purified, and the prophamphenyl-14C moiety characterized. The aglycone moiety of the polar metabolites was liberated either by methanol-HCl solvolysis or by enzyme hydrolysis with β-glucosidase or hesperidinase. The aglycone from all three procedures was derivatized, purified and characterized by NMR, ir, and mass spectral analysis. The only aglycone was the derivative of isopropyl-2-hydroxycarbanilate which was at least in part conjugated as a glycoside.  相似文献   

4.
[14C]Imidacloprid was applied to pelleted seeds of sugar beet which were then grown in pots of field soil. Leaves, roots and soil were analysed at intervals up to 97 days after planting and the distributions of parent compound and of several metabolites were quantified. At the first sampling, 21 days after application, parent imidacloprid was the main compound found in the leaves and its concentration averaged 15·2 μg g-1 fresh weight. By the 25-leaf stage, 97 days after sowing, the concentration of parent compound in the leaves had fallen to an average of 0·5 μg g-1; the metabolites and parent compound in the leaves then represented respectively 44·5% and 4·5% of the total applied radioactivity. In the root at 97 days, parent imidacloprid and its metabolites together accounted for only 0·1% of the applied activity, whilst in the soil there was 23% of parent compound and 4% as metabolites. The persistence of both parent imidacloprid and the olefinic metabolite, which has recently been shown to have higher aphicidal activity than the parent imidacloprid, explains the prolonged control of aphids observed with imidacloprid in both glasshouse and field trials. © 1998 SCI.  相似文献   

5.
To elucidate the fate of flupyrazofos [O,O-diethyl O-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)phosphorothionate] in soil, an aerobic soil metabolism study was carried out for 60 days with [14C]flupyrazofos applied at a concentration of 0·38 μg g-1 to a loamy soil. The material balance ranged from 103·5% to 86·9% and the half-life of [14C]flupyrazofos was calculated to be 13·6 days. The metabolites identified during the study were 1-phenyl-3-trifluoromethyl-5-hydroxypyrazole (PTMHP) and O,O-diethyl O-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)phosphate (flupyrazofos oxon), with maximum levels of 9·8% and 1·6% of applied radiocarbon, respectively. Evolved [14C]carbon dioxide accounted for up to 5·3% of applied radiocarbon and no volatile products were detected during the study. Non-extractable 14C-residue reached 31·6% of applied material at 60 days after treatment and radiocarbon was distributed almost evenly in humin, humic acid and fulvic acid fraction. © 1998 Society of Chemical Industry  相似文献   

6.
A laboratory study was conducted to determine the degradation rates and identify major metabolites of the herbicide metsulfuron-methyl in sterile and non-sterile aerobic soils in the dark at 20°C. Both [phenyl-U-14C]- and [triazine-2-14C]metsulfuron-methyl were used. The soil was treated with [14C]metsulfuron-methyl (0.1 mg kg−1) and incubated in flow-through systems for one year. The degradation rate constants, DT50, and DT90 were obtained based on the first-order and biphasic models. The DT50 (time required for 50% of applied chemical to degrade) for metsulfuron-methyl, estimated using a biphasic model, was approximately 10 days (9–11 days, 95% confidence limits) in the non-sterile soil and 20 days (12–32 days, 95% confidence limits) in the sterile soil. One-year cumulative carbon dioxide accounted for approximately 48% and 23% of the applied radioactivity in the [phenyl-U-14C] and [triazine-2-14C]metsulfuron-methyl systems, respectively. Seven metabolites were identified by HPLC or LC/MS with synthetic standards. The degradation pathways included O-demethylation, cleavage of the sulfonylurea bridge, and triazine ring opening. The triazine ring-opened products were methyl 2-[[[[[[[(acetylamino)carbohyl]amino]carbonyl]amino] carbonyl]-amino]sulfonyl]benzoate in the sterile soil and methyl 2-[[[[[amino[(aminocarbonyl)imino]methyl] amino]carbonyl]amino]sulfonyl]benzoate in the non-sterile soil, indicating that different pathways were operable. © 1999 Society of Chemical Industry  相似文献   

7.
Metribuzin [4-amino-6-tert-butyl-3(methylthio)-1,2,4-triazin-5(4H)-one] metabolism was studied in soybean [Glycine max (L.) Merr. Tracy]. Pulse treatment studies with seedlings and excised mature leaves showed that [5-14C]metribuzin was absorbed rapidly and translocated acropetally. In seedlings, >97% of the root-absorbed 14C was present in foliar tissues after 24 hr. In excised leaves, 50–60% of the absorbed 14C remained as metribuzin 48 hr after pulse treatment, 12–20% was present as polar metabolites, and 20–30% was present as an insoluble residue. Metabolites were isolated by solvent partitioning, and were purified by adsorption, ion-exchange, thin-layer, and high-performance liquid chromatography. The major metabolite (I) was identified as a homoglutathione conjugate, 4-amino-6-tert-butyl-3-S-(γ-glutamyl-cysteinyl-β-alanine)-1,2,4-triazin-5(4H)-one. Metabolite identification was confirmed by qualitative analysis of amino acid hydrolysis products, fast atom bombardment (FAB), and chemical ionization (CI) mass spectrometry, and by comparison with a reference glutathione conjugate synthesized in vitro with a hepatic microsomal oxidase system from rat. Minor metabolites were identified as an intermediate N-glucoside conjugate (II), a malonyl N-glucoside conjugate (III), and 4-malonylamido-6-tert-butyl-1,2,4-triazin-3,5(2H,4H)-dione (N-malonyl DK, IV) by CI and FAB mass spectrometry. Alternative pathways of metribuzin metabolism are proposed.  相似文献   

8.
Root-treated alfalfa absorbs, translocates, and metabolizes [phenyl-14C]isopropyl carbanilate ([14C]propham). After 7 days of root treatment, the distribution of radiolabel was 73% for shoots and 27% for roots. Shoots and roots were extracted and separated into the polar, nonpolar, and solid residual components using a mixture of chloroform, methanol and water. The insoluble residues accounted for approximately 40% of the 14C found in shoots and roots. The nonpolar fraction (6.1% of the radiolabel in shoots and roots) was not characterized, but was shown to be some component other than parent propham. Propham was not found in either shoots or roots. The polar metabolites were partly purified on Amberlite XAD-2. Cellulase-liberated aglycones were derivatized and separated by high-performance liquid and gas-liquid chromatography. The infrared, nuclear magnetic resonance, and mass spectral data showed that the polar metabolites of alfalfa shoots and roots were glycoside conjugates of isopropyl 2-hydroxycarbanilate (2-hydroxypropham) and isopropyl 4-hydroxycarbanilate (4-hydroxypropham). Conjugated 4-hydroxypropham accounted for 45.9% of the 14C in the shoots and 3.4% of the 14C in the roots. Conjugated 2-hydroxypropham accounted for 3.4% of the 14C in the shoots and 1.4% of the 14C in the roots.  相似文献   

9.
[14C]Monolinuron was added to soil which was then successively cropped with spinach, cress, and potatoes. Incubation was carried out in a closed system which allowed recoveries even of volatile degradation products and gave an overall recovery of 96% of the applied radioactivity at the end of the experiment. The spinach was found to contain 4.1% of the applied activity; the cress, 5.6%; old potatoes + leaves, 9.5%; new tubers, 1%; and the soil, 68.6%. The total amount of [14C]carbon dioxide liberated was 5.3%. The quantitative separation and characterization of the extractable radioactivity in spinach yielded 10.6% as unaltered monolinuron, 12% as 4-chlorophenylurea plus 4-chlorophenyl-hydroxymethylurea, 3.7% as 4-chlorophenylmethylurea, 1.4% as 4-chlorophenyl-hydroxymethyl-methoxyurea, 1.1% as 4-chlorophenyl-methoxyurea, and 71.2% as polar metabolites. Of these polar metabolites, 67.1% were cleaved with β-glucosidase, resulting in 2.9% unknown aglucone, 48.1% 4-chlorophenyl-hydroxymethyl-methoxyurea, and 16.1% 4-chlorophenyl-hydroxymethylurea. Similar results have been obtained in cress and potatoes. The soil contained 58% of monolinuron residues and 4.7?6.5% of the same types of metabolites as were found in plants. Twenty-one percent were found as polar metabolites.  相似文献   

10.
The metabolism of [14C]asulam (methyl 4-aminophenylsulphonylcarbamate), [14C] aminotriazole (1H-1,2,4-triazol-3-ylamine) and [14C]glyphosate (N-(phosphonomethyl)glycine) were assessed in Equisetum arvense L. (field horsetail). Following application of the test herbicides (4mg?0.3 °Ci herbicide/shoot) to the shoots of 2-year-old pot-grown plants, the total recovery of 14C-label after 1 week and 8 weeks was high for all three herbicides (>80-0% of applied radioactivity). Asulam was persistent (>69-7% of recovered radioactivity) in both shoots and rhizomes. Sulphanilamide, a hydrolysis product of asulam, accounted for the remainder of the recovered radioactivity. Aminotriazole showed evidence of conjugation in shoots and rhizomes. The principal 14C-labelled component in shoots was composed of high proportions of aminotriazole (>76-3%) together with the metabolites: X (ninhydrin positive), β-(3-amino-1,2,4-triazolyl-1-)α-alanine, Y (diazotization positive) and various unidentified compounds. Rhizomes generally contained lower proportions of intact aminotriazole (>59.4%) together with the metabolites X,Y and unidentified compounds. The proportion of aminotriazole did not decrease with time in shoots or rhizomes; however, the ratio of metabolite X: Y moved in favour of Y as the interval after treatment increased. Glyphosate was extensively metabolised in shoots and rhizomes to yield aminomethylphosphonic acid (AMPA) and various unidentified compounds. Differential metabolism appears to be one of the factors which may govern the persistence and toxicity of the test herbicides in E. arvense.  相似文献   

11.
Radiochemical studies of field soil treated with 14C oryzalin (3,5-dinitro-N4,N4-dipropylsulfanilamide) indicated that the compound was readily degradable. One year after soil treatment with oryzalin, 45% of the original radioactivity had dissipated, 25% was extractable, and 30% was “soil bound”. The extractable fraction contained oryzalin and several degradation products, some of which were isolated and identified. No single degradation product accounted for more than 3% of the applied oryzalin. The “soil-bound” radioactivity was extractable with hot alkali. No significant radioactive residues were detectable in either seed or forage of soybean and wheat plants. No specific metabolites of oryzalin were identified in soybean plants. Trace amounts of radioactivity found in plant tissue appeared to be associated with the various plant constituents.  相似文献   

12.
The metabolic fate of the 14C-labeled herbicide, 2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione (bioxone), in cotton (Gossypium hirsutum L. “Acala 4-42-77”) was studied using thin-layer chromatography, autoradiography, and counting. Bioxone-14C was readily metabolized by cotton tissue to 1-(3,4-dichlorophenyl)-3-methylurea (DCPMU) and 1-(3,4-dichlorophenyl)urea (DCPU). Leaf discs metabolized bioxone-14C rapidly; 12 hr posttreatment, 65% of the 14C in methanol extracts was in forms other than intact herbicide. Excised leaves treated through the petiole with either heterocyclic ring-labeled or phenyl ring-labeled herbicide contained little bioxone-14C after 1 day; DCPMU was formed early then decreased with time. DCPU accounted for 55–70% of the 14C in excised leaves 3 days posttreatment. In intact plants treated via the roots, the herbicide was rapidly metabolized in the roots to DCPMU and DCPU; little or no intact herbicide was translocated to the leaves. Little radioactivity accumulated in the roots with time; the radioactivity in the leaves accounted for 80–90% of the methanol-soluble 14C 47 days posttreatment. Most of the 14C in the leaves was recovered as DCPU (50–60%) and unidentified polar metabolite(s) which remained at the origin of the thin-layer plates (30–40%). The percentage of radioactivity which remained in cotton residue after methanol extraction increased with time. Digestion of the plant residues with the proteolytic enzyme pronase indicated that some of the nonextractable 14C may be DCPMU and DCPU complexed with proteins. Similar metabolic patterns were noted after treatment with either heterocyclic ring-labeled or phenyl ring-labeled bioxone-14C. Generally, bioxone was metabolized to DCPMU which in turn was demethylated to DCPU. The herbicide and DCPMU were 20 times as toxic as DCPU to oat (Avena sativa L.), a susceptible species.  相似文献   

13.
Sugar beet plants were grown in the field, after in-furrow application of [14C]aldicarb (3 kg of aldicarb ha?1) at planting. The ripe sugar beet plants were harvested, and the blades and petioles of the leaves were analysed separately. In the whole leaves, 15% of the 14C (all the percentages of 14C are relative to the total 14C incorporated into the whole leaves) was insoluble in ethanol+ water (1+1 by volume), 31% was organo-soluble (and thus unconjugated in the leaves), and 54% was water-soluble (mainly conjugated to plant constituents). The weights and concentrations (as aldicarb equivalents) of various identified metabolites of aldicarb, incorporated into the leaves, were determined; no aldicarb, as such, was detected.  相似文献   

14.
Sugar beet plants were grown in the field, after in-furrow application of [14C]aldicarb (3 kg of aldicarb ha?1) at planting. Some plants (the growing plants) were harvested 99 days after sowing and the rest (the ripe plants) 196 days after sowing. The percentages of the weights of [14C]aldicarb equivalents (the total aldicarb plus aldicarb sulphoxide and sulphone, plus all the other metabolites of [14C]aldicarb which contain 14C, expressed as aldicarb equivalents) incorporated into the beet plants, relative to the weight applied to the soil, were 2.8 and 1.8, respectively for the growing and ripe plants. The concentrations of [14C]aldicarb equivalents (mg kg?1 fresh weight) in the growing and ripe plants, respectively were: blades of the external leaves, 3.16 and 0.93; blades of the internal leaves, 0.63 and 0.68; petioles of the external leaves, 0.51 and 0.26; petioles of the internal leaves, 0.15 and 0.05; crowns, 0.14 and 0.15; roots, 0.16 and 0.13. The proportions of the extractable aldicarb plus aldicarb sulphoxide and aldicarb sulphone determined by gas-liquid chromatography (expressed as aldicarb equivalents) relative to [14C]aldicarb equivalents, in the external and internal leaf blades of the growing beets, were 56 and 60%, respectively; these values declined to 25 and 19%, respectively in the ripe plants. The proportion was 21 % or less in all other parts of the growing and ripe plants.  相似文献   

15.
Alfalfa plants, Moapa variety, were grown in nutrient solution containing isopropylring-[14C] carbanilate (43.8 μCi/liter propham). After 8 days, 41.2% of the radioactivity initially added to the nutrient culture was recovered; 10.9% of this was from shoots, 3.4% from roots and 26.9% from nutrient medium. Nonextracted residues accounted for 23% of the radioactivity in shoots and 62% of that in roots. The parent herbicide constituted 53 and 38% of the radioactivity extracted from shoots and roots, respectively. The balance of extracted 14C was polar metabolites which were purified and subjected to enzymatic and acid hydrolysis. Four aglycones were isolated, three of which were purified by thin-layer chromatography and characterized by mass spectrometry. The principal aglycones were: isopropyl-2-hydroxycarbanilate, isopropyl-4-hydroxycarbanilate, and 1-hydroxy-2-propylcarbanilate. The fourth aglycone was not identified.  相似文献   

16.
Male feral pigeons were dosed with ring-labeled [14C]p,p′-DDT and the tissues and droppings analyzed for total 14C, extractable 14C, and metabolites. Only 16% of an intraperitoneal dose of 1.5–2.2 mg kg?1 was voided in the droppings over 28 days; the rate of loss reached a maximum on the 14th day and then fell quickly away. The rate of removal of 14C in droppings was low in comparison to that found in the rat and the Japanese quail. When pigeons were dosed with 32–38 mg kg?1 DDT per bird, and killed after 77 days, 5.4% of the dose was eliminated in droppings and 87% was recovered in the body. The tissues and droppings from this experiment were analyzed for DDT and its metabolites. Of the 14C remaining in tissues 88% was accounted for as the apolar compounds DDE, DDT, and DDD. Approximately half of the 14C in droppings was present as DDE, DDT, and DDD, whereas 27–35% was apparently in conjugated form, extractable from aqueous solutions by ethyl acetate after prolonged acid hydrolysis. Two polar metabolites were isolated from the acid-released material. One was p,p′-DDA; the other was extractable from aqueous solution at pH 8 and was tentatively identified as a monohydroxy derivative of p,p′-DDT. DDE accounted for 93% of the 14C present as metabolites in tissues and droppings, clearly indicating the importance of this intermediate in this study. The metabolism of DDT in the feral pigeon is discussed in relation to its metabolism by other species.  相似文献   

17.
Major methanol-soluble metabolites of cisanilide (cis-2,5-dimethyl-1-pyrrolidinecarboxanilide) were isolated from excised, pulse-treated carrot and cotton leaves. They were identified as O-glucoside conjugates of primary aryl and alkyl oxidation products, 2,5-dimethyl-1-pyrrolidine-4-hydroxycarboxanilide and 2,5-dimethyl-3-hydroxy-1-pyrrolidinecarboxanilide. Comparative studies with carrot and cotton cell cultures showed similar initial pathways of cisanilide metabolism. Time-course studies with [14C-pyrrolidine]- and [14C-phenyl]cisanilide showed little, if any, cleavage of the herbicide molecule in either excised leaves or cell cultures. Quantitative differences in the metabolism of cisanilide by cell cultures and excised leaves included; a reduced capacity of cell cultures to form secondary glycoside conjugates and an increased ability of cell cultures to form methanol-insoluble residues.  相似文献   

18.
Summary. The metabolism of monuron in excised leaves of bean (Phaseolus vulgaris L., var. Black Valentine) and corn (Zea mays L., var. Batam Cross) were studied with carbonyl-14C-labelled monuron. The metabolic conversions of monuron in both plant species were exponential and followed first order reaction kinetics. The metabolism of monuron can be divided into two major pathways: demethylation and hydroxylation. At a monuron concentration of 16 ppm the hydroxylation was dominant in the bean leaves. As the concentration of monuron was increased the participation of the hydroxylation pathway became less probably due to the inhibition of enzymes involved by monuron. The demethylation pathway was not affected by higher monuron concentration. In the corn leaf, however, sequential demethylation was always the major pathway of monuron transformation and there was no inhibitory effect observed on either pathways as the concentration of monuron increased. The following radioactive metabolites were found in the alcohol extract of bean and com leaves receiving carbonyl-14C-labelled monuron: N′-(4-chlorophenyl)-N-methylurea, p-chlorophenylurea, two polypeptide complexes of monuron, one polypeptide complex of N′-(4-chlorophenyl)-N-methylurea and β-D-glucosides of N-(2-hydroxy-4-chlorophenyl) urea, N′-(2-hydroxy-4-chlorophenyl) N-methylurea, and N′-(2-hydroxy-4-chlorophenyl)-N,N-dimethylurea. In addition, one minor radioactive peak was found only in the alcohol extract of corn leaves, which yielded four unidentified radioactive metabolites after acid or enzyme hydrolysis with β-glucosidase. Métabolisme du monuron dans des feuilles excisés de maïs et de haricot  相似文献   

19.
The distribution and metabolic fate of [14C]-daminozide in silver maple and American sycamore seedlings were studied by use of autoradiography, ion-exchange chromatography, thin-layer chromatography (t.l.c.), and liquid scintillation spectrometry. Within one day after treatment with [14C]-daminozide, radioactivity was detected in all parts of the plant. The 14C concentrated in meristematic regions of the leaves. Ion-exchange and thin-layer chromatographic analyses of the 50% methanol extracts indicated that no detectable metabolites of daminozide were formed in any of the plant parts but approximately 20% of the applied 14C, most of it in the stem tissue, was not extractable by aqueous methanol.  相似文献   

20.
Metribuzin [4-amino-6-tert-butyl-3-(methylthio)-1,2,4-triazin-5(4H)-one] metabolism was studied in tomato (Lycopersicon esculentum Mill. “Sheyenne”). Pulse-treatment studies with seedlings and excised leaves showed that [5-14C]metribuzin was rapidly absorbed, translocated (acropetal), and metabolized to more polar products. Foliar tissues of 19-day-old seedlings metabolized 96% of the root-absorbed [14C]metribuzin in 120 hr. Excised mature leaves metabolized 85–90% of the petiole-absorbed [14C]metrubuzin in 48 hr. Polar metabolites were isolated by solvent partitioning, and purified by adsorption, thin-layer, and high-performance liquid chromatography. A minor intermediate metabolite (I) was identified as the polar β-d-(N-glucoside) conjugate of metribuzin. The biosynthesis of (I) was demonstrated with a partially purified UDP-glucose: metribuzin N-glucosyltransferase from tomato leaves. A possible correlation between foliar UDP-glucose: metribuzin N-glucosyltransferase activity levels and differences in the tolerance of selected tomato seedling cultivars to metribuzin was suggested. The major polar metabolite (II) was identified as the malonyl β-d-(N-glucoside) conjugate of metribuzin.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号