Comparative metabolism of 1,1-Bis-(p-chlorophenyl)-2-nitropropane (Prolan) in mouse,insects, and in a model ecosystem

¹⁴C-labeled Prolan or 1,1-bis-(p-chlorophenyl)-2-nitropropane was found to be some-what more biodegradable than DDT. This insecticide, although highly resistant to microsomal metabolism, was degraded by elimination to 1,1-bis-(p-chlorophenyl)-1-propene, and by reduction to 1,1-bis-(p-chlorophenyl)-2-aminopropane. The major degradative pathway, however, was by oxidation to 1,1-bis-(p-chlorophenyl)-2-propanone, to 1,1-bis-(p-chlorophenyl)-pyruvic acid, to bis-(p-chlorophenyl)-acetic acid, and ultimately to p,p′-dichlorobenzophenone. Therefore the ultimate degradative products of Prolan are identical to those produced from DDT.     

An evaluation of the persistence in soil of two non-chlorinated insecticides analogous to DDT

Two insecticides 1,1-bis(4-ethoxyphenyl)-2-nitrobutane (ENB) and 1,1-bis(4-ethoxyphenyl)-2-nitropropane (ENP), at concentrations varying from 0.4-40 mg kg^?1 have been examined for persistence in three soils. The proportions of the original compounds recovered decreased rapidly in a clay loam (falling to 50% in 2-6 weeks), decreased slowly in a sand (falling to 50% in 16-64 weeks) and decreased variably in a heavy clay (falling to 50% in 2-10 weeks). After the initial phase, the proportion recovered generally decreased at a slower rate. Breakdown of ENP appeared to proceed via a stepwise oxidation to give 1,1-bis(4-ethoxyphenyl)propan-2-one and 4,4′-diethoxybenzophenone. These products were readily broken down under aerobic conditions and were isolated only from waterlogged or sterile soil. Experiments under sterile conditions indicated that biological breakdown was a major factor and that chemical breakdown was specifically surface-activated.     

Paraquat-induced production of hydrocarbon gases

Paraquat dichloride (1,1′-dimethyI-4,4′-bipyridylium dichloride) induced the production of the hydrocarbon gases propane, ethane and ethylene in the xanthophycean microalga Bumilleriopsis filiformis. Formation of these gases was dependent on the light intensity and photosynthetic electron transport. Diquat dibromide (1,1′- ethylene-2,2′-bipyridylium dibromide), having a higher midpoint potential than paraquat dichloride, induced an even higher evolution of the gases. A total lack of oxygen inhibited the production of gas, while a low oxygen concentration (4–6% by volume) stimulated paraquat-induced gas formation. Culturing algae autotrophically, in a medium with a higher iron content, also increased the production of gases in the presence of the herbicide. Formation of these gases is an indication of the peroxidation of membrane lipids which, according to previous results, is correlated with a decrease of photosynthetic electron-transport activity.     

Localizing the action of two thiadiazolyl herbicidal derivatives

Enzymatically isolated leaf cells from navy beans (Phaseolus vulgaris L., cv. “Tuscola”) were used to study the effect of buthidazole (3-[5-(1,1-dimethylethyl)-1,3,4-thiadiazol-2-yl]-4-hydroxy-1-methyl-2-imidazolidinone) and tebuthiuron (N-[5-(1,1-dimethylethyl)-1,3,4-thiadiazol-2-yl]-N,N′-dimethylurea) on photosynthesis, protein, ribonucleic acid (RNA), and lipid synthesis. The incorporation of NaH¹⁴CO₃, [¹⁴C]leucine, [¹⁴C]uracil, and [¹⁴C]acetic acid as substrates for the respective metabolic process was measured. Time-course and concentration studies included incubation periods of 30, 60, and 120 min and concentrations of 0.1, 1, 10, and 100 μM of both herbicides. Photosynthesis was very sensitive to both buthidazole and tebuthiuron and was inhibited in 30 min by 0.1 μM concentrations. RNA and lipid syntheses were inhibited 50 and 87%, respectively, by buthidazole and 42 and 64%, respectively, by tebuthiuron after 120 min at 100 μM concentration. Protein synthesis was not affected by any herbicide at any concentration or any exposure time period. The inhibitory effects of buthidazole and tebuthiuron on RNA and lipid syntheses may be involved in the ultimate herbicidal action of these herbicidal chemicals.     

Accumulation of 3,3′-biflaviolin,a melanin shunt product,by tricyclazole-treated Thielaviopsis basicola

A new pigment, 3,3′-biflaviolin (3,3′-bi-2,2′,5,5′,7,7′-hexahydroxy-1,1′,4,4′-naphthoquinone), was identified from agar cultures of the fungus Thielaviopsis basicola treated with the fungal melanin inhibitor, tricyclazole. An albino mutant of T. basicola that does not form melanin or colored melanin shunt products, synthesized 3,3′-biflaviolin when treated with flaviolin. The dimerization reaction appeared to be enzymatic.     

Conversion of [14C]buturon in soil and leaching water under outdoor conditions

[¹⁴C]Buturon, a urea herbicide, was sprayed on soil and winter wheat as an aqueous formulation (2.98 kg/ha) under outdoor conditions. Three months after application, a total of 49.2% of the applied radiocarbon was recovered: 46.9% in the soil, 0.3% in the leaching water (depth > 50 cm), and 2.0% in the plants. Radioactive residues in the soil were distributed to a depth of 50 cm and decreased with increasing depth of the soil. An average of 47% of the radioactivity present in the soil could be extracted with cold chloroform; by this extraction method, the formation of artefacts was avoided. Between one and two thirds of the extracted radioactivity was unchanged buturon. In the soil extracts, the following eight conversion products were isolated and identified by combined gas chromatography/mass spectrometry: N-(p-chlorophenyl)-N-methyl-O-methyl carbamate; N-(p-chlorophenyl)-O-methyl carbamate; N-(p-chlorophenyl)-N′-methyl-N′-isobutenyl-urea; N-(p-chlorophenyl)-N′-methyl-urea, N-(p-chlorophenyl)-N′-methyl-N′-isobutenylol-urea; p-chloroaniline in “biologically bound” form; N-(p-chlorophenyl)-N′-methyl-N′-methoxyisobutenyl-urea; and N-(p-chlorophenyl)-N′-methyl-N′-ethoxyisobutenyl-urea. In the leaching water, which contained only 0.005–0.006 mg/liter of radioactive substances, the following three conversion products were isolated and identified by gas chromatography/mass spectrometry: p-chloroformanilide; N-(p-chlorophenyl)-N-methyl-O-methyl carbamate; and an N-hydroxyphenyl-N′-methyl-N′-isobutinyl-urea. The results are discussed in relation to the factors responsible for the formation of these products.     

Spectroscopic studies on the mechanisms of adsorption of paraquat by humic acid and model compounds

Changes in the relative sizes of the carboxylic absorption bands in the infrared spectra (near 1730 and 1610 cm^?1) of adsorbents before and after treatment with paraquat (1,1′-dimethyl-4,4′-bipyridylium dichloride) showed that ion exchange is the predominant mechanism for adsorption of the bipyridyl by H⁺- ion saturated preparations of a humic acid from an organic soil, by two hydroquinone polymers and by two carboxylic ion-exchange resins. Attempts to relate the extents of saturation (with adsorbate) of the exchange sites with the optical densities of the infrared bands were unsuccessful because of deviations from Beer's Law. Ultraviolet spectroscopy failed to provide evidence for charge transfer mechanisms in paraquat-humic acid complexes in aqueous systems.     

Effects of anti-ecdysteroid quaternary derivatives of azole analogues of metyrapone on the post-embryonic development of the red cotton bug (Dysdercus cingulatus F)

In order to improve the larvicidal activity of the azole analogues of metyrapone, previously found to have a strong inhibitory activity on ecdysone 20-monooxygenase (E-20-M) from the fleshfly Neobellieria bullata Parker, soft-alkylated compounds (3-(1,1-dimethyl-2-oxo-2-phenylethyl)-1-dodecanoyloxymethyl-1H-imidazolium chloride, sPIM) and (1-(1,1-dimethyl-2-oxo-2-phenylethyl)-4-dodecanoyloxymethyl-1H-1,2,4-triazolium chloride, sPTM), derivatives of phenyl-imidazolyl-metyrapone (PIM) and phenyl-1,2,4-triazolyl-metyrapone (PTM), respectively, were synthesized. Both sPIM and sPTM, designed as propesticides, inhibited E-20-M in vitro at 10(-4) M concentration, which was unexpected since they had been expected to be inactive in vitro and to gain activity only within the organism. sPTM significantly delayed the pupariation of N. bullata larvae and this effect could be reversed by the simultaneous application of 20-hydroxyecdysone (20E), supporting the hypothesis that sPTM can act by interfering with the moulting hormone system. Due to this in vitro activity, sPTM and sPIM cannot be considered to be simple drug precursors, and their structure should contain structural elements (pharmacophores) responsible for the observed biological effects. In order to examine this hypothesis, derivatives of sPTM and sPIM were synthesised in which the hydrolytically labile N(+)-CH2O(CO)- moiety was changed to the more stable N(+)-CH2CH2(CO)-group. In three new stable derivatives, a dodecylamino or a phenyl group, respectively, is attached to the carbonyl group to obtain PTM and PIM derivatives quaternised with a 2-dodecylcarbamoylethyl or a 3-oxo-3-phenylpropyl group. In one derivative, the 2-oxo-2-phenylethyl quaternising group has one fewer carbon atom. In addition to their moderate activity (LC50 = 10(-6)-10(-5) M) against the red cotton bug Dysdercus cingulatus F, they delayed development and caused developmental abnormalities, including mortality in the pharate phase, mortality during moulting and wing deformations. These symptoms and the delay in development are characteristic of known compounds inhibiting the synthesis of 20E or interfering in the moulting processes. The facts that the frequent appearance of insects with developmental abnormalities and the delay in development could be reversed by co-application of 20E indicate that the moulting system might be the site of action. We presume that the quaternary azole derivatives of PIM and PTM can themselves also interact with the moulting system.     

甜瓜黄斑病毒三亚分离物S RNA的分子特征

 甜瓜黄斑病毒（Melon yellow spot virus, MYSV）首次发生于日本,造成甜瓜和黄瓜的严重损失,Kato等系统地研究了病毒的传播方式、寄主范围、超微结构和基因组特征,认为MYSV应为番茄斑萎病毒属（Tospovirus）的1个新种［1,2］。2006年以来,台湾的西瓜［3］和黄瓜［4］上相继发现MYSV。2009年春季,古勤生在海南三亚的保护地甜瓜上发现一种新发生的病毒病,发病率30%~100%,病株出现系统性黄化坏死斑点,为MYSV侵染的典型症状,结合分子检测结果判定病原为MYSV。     

In vitro activity of sorghum-selective fluorophenyl urea herbicides

The use of N-cyclopropyl-N′-(2-fluorophenyl) urea as a selective herbicide in grain sorghum has recently been disclosed (U.S.P. 4,344,916). Evaluation of analogs of this compound has included two assays on isolated pea chloroplasts—photosynthetic electron transport and competition for atrazine binding sites. Of all the analogs studied in at least one of these assays, the most active in vitro were the N-cyclopropyl-, N-n-butyl-, and N-n-pentyl-derivatives of 2,5-difluorophenyl urea. The two in vitro assays correlated well with each other, and binding activity demonstrated a strong correlation with whole-plant phytotoxicity following postemergence application. Several postulated sorghum metabolites of N-cyclopropyl-N′-(2-fluorophenyl) urea showed weak or no activity in vitro, as would be expected from the compoud's selectivity properties.     

Photolysis of Diuron

The major photoproducts observed in the photolysis of diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] ( 2 ) in aqueous solution resulted from a heterolytic substitution of chlorine by OH (photohydrolysis). A wavelength effect was observed: at 254 nm the formation of 3-(4-chloro-3-hydroxyphenyl)-1,1-dimethylurea ( 3 ) accounted for more than 90% of the conversion, whereas when the solution was irradiated in ‘black light’ (85% of photons emitted at 365 nm, about 7% at 334 nm), the major photoproduct was 3-(3-chloro-4-hydroxyphenyl)-1,1-dimethylurea ( 4 ). The presence of methanol favoured the photoreduction into 3-(3-chlorophenyl)-1,1-dimethylurea ( 5 ). Completely different reactions were observed when 2 was irradiated in dry aerobic conditions on silica. They resulted from elimination or oxidation of methyl groups. The main photoproducts initially formed were 3-(3,4-dichlorophenyl)-1-methyl urea ( 6 ) and 3-(3,4-dichlorophenyl)-1-formyl-1-methylurea ( 7 ). In the second stage ( 6 ) was transformed into (3,4-dichlorophenyl)-urea ( 8 ) and 3-(3,4-dichlorophenyl)-1-formylurea ( 9 ); some other minor products such as monuron ( 1 ) were also identified. The formation rate of 6 and 7 was much slower on clay (montmorillonite or kaolin) than on silica. In contrast with products 6 and 8 , the formation of 7 and 9 needed the presence of oxygen: they did not appear when diuron was irradiated in deoxygenated C₂Cl₃F₃. It can be concluded that the photolysis of diuron is highly dependent on the conditions of irradiation. © 1997 SCI.     

Growth regulator inhibition of tobacco callus growth

The activity of two groups of growth regulators, substituted dinitroanilines and nitrophenylhydrazines, were evaluated in a tobacco (Nicotiana tabacum L. “X-73”) callus tissue bioassay. Molar concentrations required to inhibit fresh weight gain by 50% (I₅₀) was determined by using linear regression analysis on data obtained by testing a range of five concentrations of each chemical. All chemicals tested were inhibitory to callus tissue grown in the dark. Cell division seemed to be the primary activity inhibited. The most active of the dinitroaniline series was α,α,α-trifluoro-2,6-dinitro-N-ethyl-N-2′,6′-dichlorobenzyl-p-toluidine (I) (I₅₀ = 1.5 × 10^?10M). I and two other N-(o-halobenzyl) dinitroanilines were more active than α,α,α-trifluoro-2,6-dinitro-N-ethyl-N-2′-chloro-6′-fluorobenzyl-p-toluidine (IV), which is being developed commercially for suppression of axillary buds in tobacco. The two most active nitrophenylhydrazines tested were 1,1-dimethyl-2-(2′,6′-dinitro-3′-n-propylamino-α,α,α-trifluoro-p-tolyl)hydrazine (XVIII) and 3′,5′-dinitro-p-(2,2-diethylhydrazino)-N-methoxy-N-methylbenzamide (XIX) (I₅₀ values of 7.9 × 10^?9 and 9.3 × 10^?9M, respectively). Factors such as electronic distribution, steric hindrance, and lipid solubility were considered to influence the biological activity of the compounds tested.     

Some effects of paraquat on crop establishment in killed swards

The establishment of crops direct-drilled after various times into swards treated with paraquat (1,1′-dimethyl-4,4′-bipyridylium- 2/A) was examined. Best results with Brassica napus and B. oleracea were obtained with 1–1 kg/ha applied 7 days before drilling and 2–3 kg/ha applied 14 days before. Although delaying drilling from 7 to 14 days after application reduced the phytotoxicity, the higher dose was needed when drilling was delayed, to reduce competition from the sward regrowth. In the glasshouse, mulches of paraquat-treated herbage affected seedling growth and development of Brassica napus, Hordeum vulgare and Lolium perenne; B. napus was the most susceptible. Quelques effets du paraquat sur des cultures implantées aprés destruction d'herbages L'implantation de cultures en semis direct, apres divers intervalles de temps, dans des herbages trait6s au paraquat (l,r-diméthyl-4-4′-bipyridylium-2/4) a été examinée. Avec Brassica napus et B. oleracea, les meilleurs résultats ont été obtenus par des applications de 1,1 kg/ha et de 2,3 kg/ha, respectivement 7 jours avant et 14 jours avant le semis. Bien que le fait de porter de 7 à 14 jours le délai entre le traitement été le semis ait réduit la phytotoxicité, la dose la plus forte a été nécessaire lorsque le semis a été retardé, pour réduire la competition due à la repousse de la prairie. En serre, des paillis d'herbages traités au paraquat ont affecté la croissance et le développement de Brassica napus, Hordeum vulgare et Lolium perenne; B. napus s'est montré le plus sensible. Einige Effekte von Paraquat auf die Entwicklung von Kulturpflanzen in abgetöteten Pflanzendecken Es wurde die Entwicklung von Kulturen untersucht, die in unterschiedlichen Zeitabständen direkt in mit Paraquat (l,l'-Dimethyl-4,4′-bipyridylium-2/4) behandelte Pflanzendecken gesät wurden. Die besten Ergebnisse mit Brassica napus und B. oleracea wurden erzielt, wenn 1.1 kg/ha 7 Tage und 2 3 kg/ha 14 Tage vor der Saat gespritzt wurden.     

Mode of action of meturine

The effect of meturine on the light processes of photosynthesis was studied.Meturine is a herbicide for weed control in potato and cotton crops. It is a N-phenyl—N-hydroxy—N′-methylurea.The experiments were carried out on isolated pea and spinach chloroplasts.When examining photosystem I, reduced DPIP was used as an electron donor, whereas methyl-viologen served as an electron acceptor. When examining photosystem II, DPIP represented the electron acceptor.The obtained experimental results have pointed to the absence of the effect of meturine upon the photoreaction I.Unlike N-phenyl—N′, N′-dimethylureas (CMU, DCMU) meturine has been a very weak inhibitor of photoreaction II.The authors explain the photoreaction II inhibition of chloroplasts from plants treated with herbicidal doses of meturine by conversion of N-phenyl—N-hydroxy—N′-methylurea into Hill reaction inhibitor(s). N-Phenyl—N′-methylurea can be one of such meturine metabolites.Meturine herbicidal action is accounted for by meturine transformation into Hill reaction inhibitor(s) in the plant tissues.     

Studies on the action of chlordimeform in cockroaches

The effects of chlordimeform [N-(2-methyl-4-chlorophenyl)-N′,N′-dimethylformamidine] on amine regulatory mechanisms in insects were studied. Chlordimeform inhibits monoamine oxidase (MAO) from cockroach heads in vitro, and the MAO substrates serotonin and norepinephrine accumulate in poisoned insects in vivo. Chlordimeform synergizes the toxicity of tryptamine, another MAO substrate. The significance of these findings in relation to the mode of action of chlordimeform is discussed.     

Anaerobic microbial degradation of diuron by pond sediment

Anaerobic degradation of the herbicide diuron, 3-(3,4-dichlorophenyl-1,1)dimethylurea, was studied. Enrichment cultures were established with seven different media in the presence of diuron (40 mg/liter). Media included combinations of sediment extract, mineral salts, and various organic amendments. Cultures were inoculated with aliquots of sediment collected from a pond previously treated with diuron and were maintained under an atmosphere of 95% N₂ and 5% CO₂. All enrichment cultures completely degraded diuron in 17–25 days. In all cultures showing diuron degradation, the product identified as 3-(3-chlorophenyl)-1,1-dimethylurea appeared in approximately stoichiometric amounts. Reinjection of diuron into each culture after 26 days resulted in rapid degradation of the parent herbicide with the appearance of proportionately more 3-(3-chlorophenyl)-1,1-dimethylurea. No other product was detected after 80 days in culture and the metachloro derivative was not degraded further during this time.     

Inhibition of DNA synthesis in boll weevils (Anthonomus grandis boheman) sterilized by dimilin

When boll weevils, Anthonomus grandis Boheman, were treated with dimilin (N-(4-chlorophenyl)-N′-(2,6-difluorobenzoyl)urea), the biosynthesis of deoxyribonucleic acid was inhibited in the female, but neither ribonucleic acid nor protein synthesis was affected. Treated males showed a difference in effect in lipoprotein synthesis, whereas no significant difference was demonstrated with females. Testicular growth was inhibited in some of the males. Diminishment of sexual function may therefore result in part from inhibition of biosynthesis of DNA by dimilin.     

Metabolism of 1,1-bis-(p-ethoxyphenyl)-2-nitropropane in the house fly and the cluster caterpillar

Some aspects of the metabolism of a new insecticide, 1,1-bis-(p-ethoxyphenyl)-2-nitropropane have been investigated in the house fly, Musca domestica and the cluster caterpillar, Spodoptera litura. In the house fly the compound was deethylated and after 24 hr exposure, 1-(p-ethoxyphenyl)-1-(p-hydroxyphenyl)-2-nitropropane and 1,1-bis-(p-hydroxyphenyl)-2-nitropropane were isolated. From evidence given below it is probable that conjugates of these compounds were also present. Feeding of the insecticide to S. litura resulted in the excretion of mainly unchanged insecticide although a small percentage was converted to a polar compound tentatively identified as 1,1-bis-(p-hydroxyphenyl)-2-propanone.     

Removal of paraquat and atrazine from water by montmorillonite‐(Ce or Zr) phosphate cross‐linked compounds

The adsorption of paraquat (1,1′‐dimethyl‐4,4′‐bipyridilium dichloride) and atrazine (6‐chloro‐N ²‐ethyl‐N ⁴‐isopropyl‐1,3,5‐triazine‐2,4‐diamine) from aqueous solution onto two montmorillonite‐(Ce or Zr) phosphate cross‐linked compounds at different temperatures (288 K and 308 K) has been studied using batch experiments. The adsorption isotherms obtained for paraquat on both adsorbents may be classified as H‐type of the Giles classification, which suggests that paraquat molecules are strongly adsorbed on the samples. For the adsorption of atrazine, L‐type isotherms were obtained for both montmorillonite‐(Ce or Zr) phosphate compounds, which suggests that these compounds have a medium affinity for this herbicide. The increase in temperature from 288 K to 308 K did not have any clear effect on the adsorption process of paraquat on either adsorbent whereas atrazine adsorption decreased slightly as temperature increased, possibly due to a mainly physical process. Fourier transform infrared (FTIR) spectroscopic studies revealed that at the pH generated by the adsorbents, the cationic herbicide interacted to a greater extent with the negatively charged surface of the adsorbents than did atrazine. For both herbicides, the Ce‐montmorillonite adsorbent showed a higher adsorption capacity than the Zr‐montmorillonite adsorbent. © 2000 Society of Chemical Industry     

Chlordimeform: Uncoupling activity against rat liver mitochondria

The pesticide chlordimeform [N′-(4-chloro-o-tolyl)-N,N-dimethylformamidine] at 0.04 μmoles/mg protein uncouples 50% of respiratory-chain phosphorylation of rat liver mitochondria. This uncoupling activity depends on mitochondrial protein concentration and can be reversed either by the addition of bovine serum albumin or by washing. The normal inhibition of state 3 respiration by oligomycin and atractylate is completely reversed by chlordimeform. Uncoupling concentrations of chlordimeform elicit high adenosine triphosphatase activity. This activity is blocked by the above inhibitors of mitochondrial energy-transfer reactions. Evidence is presented which shows that unprotonated chlordimeform is the form effective in uncoupling. It is concluded that chlordimeform is an uncoupling agent with a potency and site of action close to but probably not identical to that of the classical uncoupler 2,4-dinitrophenol.