RESUMO
Wild panicgrass (Panicum miliaceum L. var. ruderale kit.) is an annual grass weed that primarily occurs in maize fields. Nicosulfuron is a widely used selective herbicide that effectively controls gramineous weeds in maize fields. However, owing to its long-term and extensive application, the control of P. miliaceum has been substantially reduced. The objective of this study was to determine the resistance pattern to ALS inhibitors in P. miliaceum and investigate the underlying resistance mechanisms. These are important for guiding the prevention and eradication of resistant weeds. Whole plant bioassays showed P. miliaceum had evolved high levels of resistance to nicosulfuron and multiple resistance to atrazine and mesotrione. The ALS gene sequence results indicated the absence of mutations in the resistant population. Additionally, there was no significant difference found in the inhibition rate of the ALS enzyme activity (I50) between the resistant and sensitive populations. Following the application of malathion the resistant P. miliaceum population became more sensitive to nicosulfuron. At 96 h after application of nicosulfuron, glutathione-S-transferase activity in the resistant population was significantly higher than that in the susceptible population. The study reveals that the main cause of resistance to ALS inhibitor herbicide in P. miliaceum is likely increased metabolism of herbicides. These findings may assist in devising effective strategies for preventing and eliminating resistant P. miliaceum.
Assuntos
Acetolactato Sintase , Herbicidas , Panicum , Panicum/metabolismo , Herbicidas/farmacologia , Compostos de Sulfonilureia/farmacologia , Piridinas/farmacologia , Zea mays , Resistência a Herbicidas/genética , Acetolactato Sintase/metabolismo , Proteínas de Plantas/genéticaRESUMO
Echinochloa phyllopogon is a self-pollinating allotetraploid weed and a serious threat to global rice production. One sensitive and three multiple-resistant populations collected from two provinces of Northeast China were used to analyze the mechanism of multiple resistance of E. phyllopogon to penoxsulam, metamifop, and quinclorac. Compared with the sensitive population LN12, LN1 showed higher resistance to these three herbicides; LN24 showed medium resistance to penoxsulam and metamifop and higher resistance to quinclorac (274-fold); HLJ4 showed low resistance to penoxsulam and high resistance to metamifop and quinclorac. Target sequence analysis showed no mutations in acetolactate synthase or acetyl-CoA carboxylase genes. In-vitro enzyme activity analysis showed that the activity of the target enzyme of multiple herbicide-resistant populations was similar to that of the sensitive population. The P450 inhibitor, malathion, noticeably increased the sensitivity of LN1, LN24, and HLJ4 to penoxsulam, LN1 to metamifop, and HLJ4 to quinclorac. Under all four treatments, the GSTs activities of resistant and sensitive populations showed an increasing trend from day 1 to day 5, but the sensitivity and activity of GSTs were higher in the multiple-resistant population than that in the sensitive population LN12. This study identified the development of multiple-resistant E. phyllopogon populations that pose a serious threat to rice production in rice fields in Northeast China, preliminarily confirming that multiple-resistance was likely due to non-target-site resistance mechanisms. These populations of E. phyllopogon are likely to be more difficult to control.
Assuntos
Echinochloa , Herbicidas , Resistência a Herbicidas/genética , Echinochloa/genética , Ácidos Indolacéticos , Herbicidas/farmacologia , Acetil-CoA Carboxilase/genéticaRESUMO
Monochoria korsakowii is an increasingly significant threat to rice production across China, particularly in Liaoning province. Few studies have reported herbicide resistance in M. korsakowii, and resistance status and mechanisms are poorly understood. Here, thirty field populations of M. korsakowii were collected from 11 rice-growing regions of Liaoning, and 97% of populations had evolved resistance to bensulfuron-methyl (BM), with majority (24 of 28) showing high resistance levels (RI > 10). The first in-depth analysis of molecular features of AHAS1 and AHAS2 in BM-resistant populations showed that four Pro197 mutations (Pro197 to His, Ala, Leu or Ser) in AHAS1 and one mutation (Pro197Ser) in AHAS2 were identified. Notably, novel double Pro197Ser mutations co-occurred in both AHAS1 and AHAS2 in the most resistant line LN-20. Furthermore, resistant mutants were used to investigate the effect of Pro197 mutations on AHAS functionality, binding modes, gene expression and cross-resistance in M. korsakowii. All the detected Pro197 mutations considerably reduced in vitro AHAS sensitivity to BM by weakening hydrogen bonds and hydrophobic interactions in the predicted BM-AHAS complexes, especially the double Pro197Ser mutations. This novel resistance mutation combination slightly impacted the extractable AHAS activity, and increased the affinity and catalytic rate of pyruvate. Also, the AHAS expression level was significantly up-regulated. Moreover, all mutations provided resistance only to other sulfonylureas herbicides but not triazolopyrimidine or pyrimidinyl-benzoates herbicides. In conclusion, bensulfuron-methyl resistance in M. korsakowii was grim in Liaoning, China, and amino acid mutations on AHAS isozymes were the primary resistance mechanism. Double Pro197Ser mutations in both AHAS1 and AHAS2 confer higher herbicide resistance than single mutations in AHAS1. Thus, this work deepens our understanding of resistance status and mechanisms of M. korsakowii.
Assuntos
Acetolactato Sintase , Herbicidas , Acetolactato Sintase/genética , Compostos de Sulfonilureia/farmacologia , Herbicidas/farmacologia , Resistência a Herbicidas/genética , ChinaRESUMO
Cucumber corynespora leaf spot, caused by Corynespora cassiicola, is the primary disease of cucumber leaves in greenhouses in China. Fludioxonil is a phenylpyrrole fungicide that inhibits C. cassiicola growth. We studied the sensitivity of 170 isolates of C. cassiicola to fludioxonil and evaluated resistance risk. All of the isolates were sensitive to fludioxonil. The EC50 values ranged from 0.082 to 0.539 µg/mL with a mean of 0.207 ± 0.0053 µg/mL. Laboratory-created mutants with a high resistance factor to fludioxonil were genetically stable after 10 transfers and showed positive cross-resistance to iprodione and procymidone but not to azoxystrobin, carbendazim, pydiflumetofen, and prochloraz. There was no significant difference in mycelial growth and temperature adaptation between the mutant s and the sensitive isolates, except for pathogenicity and sporulation. The resistant isolates accumulated less glycerol than their parental isolates and were more sensitive to osmotic stress. The histidine kinase activity of the sensitive isolates was significantly inhibited compared to that of the resistant mutants. Sequence alignment of the histidine kinase gene CCos revealed that the mutants RTL4, RXM5, and RFS102 had point mutations at different sites that resulted in amino acid changes at G934E, S739F, and A825P in the CCos protein. The mutant RFS102 had an alanine deletion at site 824. After fludioxonil treatment, CCos expression by RFS20 was significantly lower than that of the parental isolate. Our findings demonstrate that C. cassiicola exhibits moderate resistance to fludioxonil.
Assuntos
Cucumis sativus , Farmacorresistência Fúngica , Histidina Quinase , Farmacorresistência Fúngica/genética , Medição de RiscoRESUMO
Recently, the herbicide fomesafen has frequently failed to control the troublesome weed Ipomoea nil in soybean fields in Liaoning Province, China. Hence, we collected 10 suspected resistant populations and evaluated their sensitivity to fomesafen. The results revealed various degrees of Ipomoea nil resistance to fomesafen, with a resistance index of 2.88 to 22.43; the highest value occurred in the LN3 population. Therefore, the mechanisms of the resistance in LN3 to fomesafen were explored. After fomesafen treatment, the expression levels of InPPX1 and InPPX2 genes were 4.19- and 9.29-fold higher, respectively, in LN3 than those in the susceptible (LN1) population. However, mutations and copy number variations were not detected between the two populations. Additionally, malathion pretreatment reduced the dose necessary to halve the growth rate of LN3 by 58%. Liquid chromatography with tandem mass spectrometry demonstrated that metabolism of fomesafen was significantly suppressed by malathion. Moreover, LN3 displayed increased reactive oxygen species scavenging capacity, which was represented by higher superoxide dismutase and peroxidase activities after fomesafen application than those in LN1. An orthogonal partial least squares-discriminant analysis revealed that the high resistance in LN3 could be attributed mainly to enhanced metabolism. Fortunately, the fomesafen-resistant I. nil remained sensitive to 2,4-D-ethylhexylester and bentazon, providing methods for its control.
Assuntos
Herbicidas , Ipomoea nil , Ipomoea nil/metabolismo , Variações do Número de Cópias de DNA , Malation , China , Herbicidas/farmacologia , Herbicidas/metabolismoRESUMO
Corynespora cassiicola is the causal agent of cucumber Corynespora leaf spot, which affects many economically important plant species. Chemical control of this disease is hampered by the common development of fungicide resistance. In this study, 100 isolates from Liaoning Province were collected, and their sensitivity to 12 fungicides was determined. All the isolates (100%) were resistant to trifloxystrobin and carbendazim, and 98% were resistant to fluopyram, boscalid, pydiflumetofen, isopyrazam, and fluxapyroxad. However, none were resistant to propiconazole, prochloraz, tebuconazole, difenoconazole, and fludioxonil. The Cytb gene of trifloxystrobin-resistant isolates encoded the G143A mutation, whereas the ß-tubulin gene of carbendazim-resistant isolates encoded the E198A and E198A and M163I mutations. Mutations in SdhB-I280V, SdhC-S73P, SdhC-H134R, SdhD-D95E, and SdhD-G109V were associated with resistance to the succinate dehydrogenase inhibitors (SDHIs). Trifloxystrobin, carbendazim, and fluopyram were barely effective on the resistant isolates, whereas fludioxonil and prochloraz were effective on the isolates that were resistant to the quinone outside inhibitors (QoIs), SDHIs, and benzimidazoles. Ultimately, this study demonstrates that fungicide resistance seriously threatens the effective control of Corynespora leaf spot.
Assuntos
Cucumis sativus , Fungicidas Industriais , Estrobilurinas/farmacologia , Fungicidas Industriais/farmacologia , Succinato Desidrogenase/genética , Benzimidazóis/farmacologiaRESUMO
Ipomea purpurea (L.) Roth. reduces dry land crop yield and quality in Northeast China, especially in Liaoning Province. Frequent use of thifensulfuron-methyl in recent years has resulted in herbicide resistance in I. purpurea. We evaluated resistance levels of I. purpurea to thifensulfuron-methyl, an acetolactate synthase (ALS) inhibitor, in Liaoning Province and further investigated the resistance mechanisms. The results showed that 15 populations of I. purpurea have evolved up to 5.81-34.44-fold resistance to thifensulfuron-methyl, compared to the susceptible population (S), among which LN3 was the most resistant. DNA sequencing of the ALS gene in susceptible and resistant populations did not reveal any target site mutations that could be associated with resistance to thifensulfuron-methyl in I. purpurea. Additionally, no significant difference was detected between the in vitro ALS activity of LN3 and S. The GR50 of LN3 decreased sharply by 47% when malathion (a P450 inhibitor) was applied with thifensulfuron-methyl. Absorption of thifensulfuron-methyl by LN3 was equal to that of S; however, LN3 metabolized the herbicide significantly faster. This was repressed after the inhibition of P450s activity. Collectively, our results confirmed that I. purpurea in Liaoning Province has developed resistance to thifensulfuron-methyl and implied that the resistance was conferred by the increase in detoxification mediated by P450s. Furthermore, LN3 was sensitive to fluroxypyr, which can be used as an alternative to control I. purpurea.
Assuntos
Acetolactato Sintase , Herbicidas , Ipomoea , Acetolactato Sintase/metabolismo , Resistência a Herbicidas/genética , Herbicidas/farmacologia , Ipomoea/genética , Ipomoea/metabolismo , Proteínas de Plantas/genética , Compostos de Sulfonilureia , TiofenosRESUMO
Silybum marianum L. is a therapeutic plant belonging to the family Asteraceae, which has exhibited silymarin, a principal component used to cure various physiochemical disorders. The study appraised the phytochemical analysis, antioxidant activity and chemical analysis of an extract from the seed, stem and leaves. Qualitative and quantitative phytochemical analysis was evaluated by the Folin-Ciocalteu reagent method and aluminum chloride colorimetric method, respectively. While the antioxidant activity was determined by using 1,1-diphenyl-2-picrylhydrazyl (DPPH) and acetate buffer in ferric chloride (FRAP) assay, respectively, the chemical profile was evaluated by Gas Chromatography-Mass Spectrometry (GC-MS) assay. The study outcomes identified that alkaloids, glycosides, flavonoids, terpenoids, steroids and catcholic tannins were present in seed, stem and leaves extracts except for saponins and Gallic tannins. Whereas, phenols were absent only in seed extract. Quantitative analysis revealed the presence of phenols and flavonoids in appreciable amounts of 21.79 (GAE/g), 129.66 (QE/g) and 17.29 (GAE/g), 114.29 (QE/g) from the leaves and stem extract, respectively. Similarly, all extracts expressed reasonable DPPH inhibition (IC50) and FRAP reducing power such as 75.98, 72.39 and 63.21% and 46.60, 51.40 and 41.30 mmol/g from the seeds, stem and leaves extract, respectively. Additionally, chemical analysis revealed the existence of 6, 8 and 9 chemical compounds from the seeds, stem and leaves extract, respectively, corresponding to 99.95, 99.96 and 98.89% of the whole extract. The chemical compound, Dibutyl phthalate was reported from all extracts while, Hexadecanoic acid, methyl ester and Silane, (1,1-dimethylethyl), dimethyl (phenylmethoxy) were reported only from the seed and leaves extract. Moreover, Methyl stearate was also a major compound reported from all extracts except for seed extract. It is demonstrable that extracts from different parts of S. marianum possess significant antioxidant activity, as well as valuable chemical compounds accountable for therapeutic effects that might be incorporated as an alternative to synthetic chemical agents.
Assuntos
Antioxidantes , Silybum marianum , Antioxidantes/química , Flavonoides/análise , Flavonoides/farmacologia , Cromatografia Gasosa-Espectrometria de Massas , Fenóis/análise , Compostos Fitoquímicos/química , Extratos Vegetais/química , TaninosRESUMO
Acetohydroxy acid synthase (AHAS)-inhibiting herbicides are one of the most commonly used herbicides for controlling the growth of Sagittaria trifolia L. in paddy fields in Northeastern China. In this study, we collected five suspected resistant populations of S. trifolia (R1-R5) from three different provinces of Northeastern China. The results of whole-plant bioassays revealed that those populations showed high level of resistance to bensulfuron-methyl with resistance index (GR50 R/S) ranging from 39.90 to 88.50. The results of AHAS-activity assays were consistent with the results of the whole-plant bioassays. The AHAS gene analysis showed that R2 and R3 populations contained Pro-197-Leu mutations that were highly resistant to penoxsulam; R1 and R4 populations contained Pro-197-Ser mutations that were highly resistant to bispyribacsodium; R5 population contained Trp-574-Leu mutation that showed high resistance to IMI, PT, PTB and SU herbicides. The AHAS with resistance mutations showed less sensitivity to feedback inhibition by BCAAs and R genotypes had increased free BCAAs.
Assuntos
Acetolactato Sintase , Herbicidas , Sagittaria , Acetolactato Sintase/genética , China , Resistência a Herbicidas/genética , Herbicidas/farmacologia , MutaçãoRESUMO
Thirty-four novel compounds were synthesized using chesulfamide (N-(2-trifluoromethyl-4-chlorophenyl)-2-oxocyclohexyl sulfonamide), a high-profile fungicide, as the lead compound, and their structures were characterized by 1H NMR, 13C NMR, MS and elemental analysis. Additionally, the structure of (1S,2R)-2-((3-bromophenethyl)amino)-N-(4-chloro-2-trifluoromethylphenyl)cyclohexane-1-sulfonamide (IV-9) was confirmed by X-ray single crystal diffraction. The mycelium inhibition tests, spore germination inhibition tests, tomato pot tests and field trials were performed against strains of B. cinerea. Bioassay results showed that most of target compounds had good fungicidal activity against B. cinerea, in particular, IV-9 exhibited similar or superior effects to procymidone, boscalid and pyrisoxazole in all in vitro and in vivo tests. Moreover, there was no positive cross-resistance found between the compound IV-9 and eight commercial fungicides (azoxystrobin, boscalid, chlorothalonil, diethofencarb, fludioxonil, procymidone, pyrimethanil and pyrisoxazole) in the cross-resistance validation test performed by an innovative method.
Assuntos
Botrytis/efeitos dos fármacos , Desenho de Fármacos , Fungicidas Industriais/farmacologia , Sulfonamidas/química , Cristalografia por Raios X , Farmacorresistência Fúngica/efeitos dos fármacos , Fungicidas Industriais/síntese química , Fungicidas Industriais/química , Testes de Sensibilidade Microbiana , Conformação Molecular , Pirimidinas/farmacologia , Relação Estrutura-Atividade , Sulfonamidas/síntese química , Sulfonamidas/farmacologiaRESUMO
Brevicoryne brassicae is a problematic pest in cabbage and other field crops. Synthetic pesticides are used to control this pest, but they are injurious for human health and the environment. The present study aimed to purify and identify the active compounds from Citrullus colocynthis leaves with an appraisal of their efficacy against B. brassicae. Separation and purification were performed via different chromatographic techniques. Molecular analysis and chemical structures were recognized by mass spectrum (MS) and nuclear magnetic resonance (NMR), respectively. Moreover, in vitro and in vivo aphicidal activity was assessed using various concentrations, i.e., 6.25, 12.5, 25 and 50 µg/mL at 12, 24, 48 and 72 h exposure. The outcome shows that mass spectrum analyses of the purified compounds suggested the molecular formulae are C30H50O and C29H50O, C29H48O. The compounds were characterized as fernenol and a mixture of spinasterol, 22,23-dihydrospinasterol by 1H-NMR and 13C-NMR spectrum analysis. The toxicity results showed that the mixture of spinasterol and 22,23-dihydrospinasterol showed LC50 values of 32.36, 44.49 and 37.50 µg/mL by contact, residual and greenhouse assay at 72 h exposure, respectively. In contrast, fernenol recorded LC50 values as 47.99, 57.46 and 58.67 µg/mL, respectively. On the other hand, spinasterol, 22,23-dihydrospinasterol showed the highest mortality, i.e., 66.67%, 53.33% and 60% while, 30%, 23.33% and 25% mortality was recorded by fernenol after 72 h at 50 µg/mL by contact, residual and greenhouse assay, respectively. This study suggests that spinasterol, 22,23-dihydrospinasterol are more effective against B. brassicae which may be introduced as an effective and suitable substitute of synthetic chemical pesticides.
Assuntos
Afídeos/efeitos dos fármacos , Citrullus colocynthis/química , Inseticidas/toxicidade , Folhas de Planta/química , Sitosteroides/toxicidade , Estigmasterol/análogos & derivados , Triterpenos/toxicidade , Animais , Inseticidas/análise , Inseticidas/isolamento & purificação , Espectroscopia de Ressonância Magnética , Espectrometria de Massas , Extratos Vegetais/química , Extratos Vegetais/isolamento & purificação , Extratos Vegetais/toxicidade , Sitosteroides/análise , Sitosteroides/química , Sitosteroides/isolamento & purificação , Estigmasterol/análise , Estigmasterol/química , Estigmasterol/isolamento & purificação , Estigmasterol/toxicidade , Triterpenos/análise , Triterpenos/química , Triterpenos/isolamento & purificaçãoRESUMO
To develop more valuable and effective fungicide candidates, a novel series of 3,4-dichloroisothioxazole-based cycloalkylsulfonamides were synthesized and their structures were identified by 1H NMR, 13C NMR, MS and elemental analysis. Compound 3k was further confirmed by X-ray single crystal diffraction. The in vitro bioassay results demonstrated that the target compounds showed significant fungicidal activity on mycelial growth and spore germination of Botrytis cinerea. Especially, compound 3j, with prominent inhibition effect on mycelial with EC50 and EC80 values of 1.4 and 23.7⯵g/mL respectively, was comparable to the selected commercial fungicide. Moreover, at 50⯵g/mL, the inhibition rate of compound 3j on spore germination was recorded up to 89.7%. The further in vivo bioassay results indicated compound 3j continued to show high control effect on tomato leaves, flowers and fruit at 200⯵g/mL, with control efficiencies of 94.3%, 89.3% and 91.9%, respectively. The structure-activity relationship showed that the compound with a five-membered ring possessed the best activity after the introduction of the active fragment of the 3,4-dichloroisothioxazole, provided a valuable idea for further creation of new fungicides.
Assuntos
Antifúngicos/farmacologia , Botrytis/efeitos dos fármacos , Fungicidas Industriais/farmacologia , Sulfonamidas/farmacologia , Tiazóis/farmacologia , Antifúngicos/síntese química , Antifúngicos/química , Relação Dose-Resposta a Droga , Fungicidas Industriais/síntese química , Fungicidas Industriais/química , Testes de Sensibilidade Microbiana , Estrutura Molecular , Relação Estrutura-Atividade , Sulfonamidas/síntese química , Sulfonamidas/química , Tiazóis/químicaRESUMO
Chelidonine (CHE) is a major bioactive constituent of greater celandine, a plant used in traditional herbal medicines. CHE has widely been used as an analgesic in clinical settings. We evaluated the inhibitory effects of CHE on human cytochrome P450 enzymes. CHE produced time-, concentration-, and NADPH-dependent inhibition of CYP2D6, with K I and k inact values of 20.49 µM and 11.05 min -1 , respectively. Approximately 76% of CYP2D6 activity was suppressed after 9 minute incubation with CHE (50 µM). The loss of enzyme activity was not restored following dialysis. The estimated partition ratio of the inactivation was about 156. Quinidine, a competitive inhibitor of CYP2D6, attenuated the CHE-mediated enzyme inactivation, while glutathione and catalase/superoxide dismutase did not markedly ameliorate the inhibitory effect. Upon oxidation using potassium ferricyanide, the 15.1% activity of CYP2D6 was restored. These findings indicate that CHE acted as a mechanism-based inactivator of CYP2D6 and the observed effects may induce potential drug-drug interactions.
Assuntos
Benzofenantridinas/química , Inibidores do Citocromo P-450 CYP2D6/química , Citocromo P-450 CYP2D6/química , HumanosRESUMO
Botrytis cinerea is an economically important fungal pathogen with a host range of over 200 plant species. Unfortunately, gray mold disease caused by B. cinerea has not been effectively controlled because of its high risk for fungicide resistance development. As a part of our ongoing efforts to develop novel sulfonamides as agricultural fungicides against Botrytis cinerea, we introduced 2-aminoethanesulfonic acid (taurine) substructure, designed and synthesized a series of novel 2-substituted acylaminoethylsulfonamides. The newly synthesized sulfonamides were evaluated in vitro and in vivo for their fungicidal activity against Botrytis cinerea, of which the 2-ethoxyacetylamide derivative (V-A-12, EC50â¯=â¯0.66â¯mg·L-1) exhibited the highest potency in vitro and superior fungicidal activity compared with procymidone (EC50â¯=â¯1.06â¯mg·L-1). In vivo bioassay indicated that compound V-A-12 could be effective for the control of tomato gray mold. Moreover, the structure-activity relationship of these sulfonamides was analyzed by establishing a three-dimensional quantitative structure-activity relationship (3D-QSAR) model, which can provide guidance for the development of sulfonamides as fungicides. Finally, the effeicacy of sulfonamide derivatives was again verified in the activity evaluation against resistant Botrytis cinerea strains. These results further enhance the development value of 2-substituted acylaminoethylsulfonamides to control the tomato gray mold.
Assuntos
Botrytis/efeitos dos fármacos , Fungicidas Industriais/farmacologia , Sulfonamidas/farmacologia , Fungicidas Industriais/síntese química , Fungicidas Industriais/química , Solanum lycopersicum/efeitos dos fármacos , Solanum lycopersicum/microbiologia , Estrutura Molecular , Folhas de Planta/efeitos dos fármacos , Folhas de Planta/microbiologia , Relação Quantitativa Estrutura-Atividade , Eletricidade Estática , Relação Estrutura-Atividade , Sulfonamidas/síntese química , Sulfonamidas/químicaRESUMO
To preliminarily study the law of natural dissipation and the relation to human health of a new insecticide (afidopyropen), the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method and a UHPLC-MS/MS system were used to extract and detect the afidopyropen and its metabolite (M440I007) from cucumber and nectarine. The limits of quantitation (LOQs) of both target compounds in two matrixes were reduced to 0.0001â¯mg/kg. Dissipative dynamics experiments indicated that afidopyropen residue dissipation is more consistent with a two-compartment kinetic model than a first-order kinetic model whether in cucumber or nectarine. The half-lives were less than 1.1 and 2.0 days in the distribution phase and up to 9.9 and 27.7 days in the elimination phase in cucumber and nectarine, respectively. The correlation coefficients were 0.9620, 0.9391, and 0.9923 for cucumber and 0.9676 and 0.9985 for nectarine from different locations. M440I007 initially increased rapidly, reached a maximum at 2 days, and then decreased gradually over time. Finally, dietary risk assessment indicated that the mixed residues of afidopyropen and M440I007 at the recommended dosage would not cause health concerns in population.
Assuntos
Cucumis sativus/metabolismo , Inocuidade dos Alimentos , Frutas/metabolismo , Compostos Heterocíclicos de 4 ou mais Anéis/metabolismo , Compostos Heterocíclicos de 4 ou mais Anéis/farmacocinética , Inseticidas/metabolismo , Inseticidas/farmacocinética , Lactonas/metabolismo , Lactonas/farmacocinética , Cromatografia Líquida de Alta Pressão , Compostos Heterocíclicos de 4 ou mais Anéis/análise , Humanos , Inseticidas/análise , Cinética , Lactonas/análise , Conformação Molecular , Medição de Risco , Software , Espectrometria de Massas em TandemRESUMO
Sagittaria trifolia is a medicinal foodstuff of China and East Asia belonging to the family Alismataceae. Samples of S. trifolia tubers were collected from Meihekow, Siping, Jilin, Harbin and Wuchang from Northeast China. The current study was aimed to evaluate the qualitative and quantitative analysis, antioxidant activity, biochemical analysis and chemical composition of different populations of S. trifolia. By using Folin-Ciocalteu, aluminium chloride colourimetric and 1,1-diphenyl-1-picrylhydrazyl (DPPH), total phenol and flavonoids content and antioxidant activity was analysed. Furthermore, chemical composition, biochemical analysis and mineral substances were also determined. The results showed the presence of flavonoids, phenols, saponins, tannins, glycosides and steroids except for alkaloids and terpenoids by qualitative analysis. Quantitative analysis revealed that highest total phenol, flavonoids content and antioxidant potential identified from Meihekow, i.e., 2.307 mg GAE/g, 12.263 mg QE/g and 77.373%, respectively. Gas chromatography-mass spectrometry results showed the presence of 40 chemical compounds corresponding to 99.44% of total extract that might be responsible for antioxidant properties. Mineral and biochemical analysis revealed the presence of calcium, magnesium, potassium, sodium, iron, copper, zinc and, carbohydrate, protein, fibre and fat contents, respectively. Interestingly, all S. trifolia populations collected from different locations possess similar composition. The dietary values, phytoconstituents, antioxidant activities and nutritional and curative chemical compounds of S. trifolia are beneficial for the nutritherapy of human beings.
Assuntos
Cromatografia Gasosa-Espectrometria de Massas/métodos , Metanol/química , Compostos Fitoquímicos/análise , Sagittaria/química , Compostos de Bifenilo/química , China , Flavonoides/química , Fenóis/química , Picratos/químicaRESUMO
In order to explore more efficient sulfonamides against Botrytis cinereal, 36 novel cyclohexylsulfonamides were synthesized by N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (EDCI) and 1-hydroxybenzotriazole (HOBt) condensation reaction using chesulfamide as a lead compound, introducing thiazole and pyrazole active groups. Their structures were characterized by 1H-NMR, 13C-NMR, mass spectrum (MS), and elemental analysis. Compound III -31 was further confirmed by X-ray single crystal diffraction. The in vitro and in vivo fungicidal activities against B. cinerea were evaluated by three bioassay methods. The results of mycelial growth demonstrated that median effective concentration (EC50) values of nine compounds were close to boscalid (EC50 = 1.72 µg/mL) and procymidone (EC50 = 1.79 µg/mL) against B. cinerea (KZ-9). In the spore germination experiment, it was found that compounds III-19 and III-31 inhibited germination 93.89 and 98.00%, respectively; at 10 µg/mL, they approached boscalid (95.97%). In the tomato pot experiment, the control effects of two compounds (III-21 and III-27) were 89.80 and 87.90%, respectively, at 200 µg/mL which were significantly higher than boscalid (81.99%). The structure-activity relationship (SAR) was also discussed, which provided a valuable idea for developing new fungicides.
Assuntos
Botrytis/efeitos dos fármacos , Fungicidas Industriais/química , Sulfonamidas/química , Botrytis/patogenicidade , Fungicidas Industriais/síntese química , Fungicidas Industriais/farmacologia , Relação Estrutura-Atividade , Sulfonamidas/síntese química , Sulfonamidas/farmacologia , Tiazóis/síntese química , Tiazóis/químicaRESUMO
The fate of tetraconazole enantiomers in strawberries during wine-making process was studied. The residues were determined by ultra-performance convergence chromatography tandem triple quadrupole mass spectrometry after each process steps. Results indicated that there was significant enantioselective dissipation of tetraconazole enantiomers during the fermentation process. And (-)-tetraconazole degraded faster than (+)-tetraconazole. The half-lives of (-)-tetraconazole and (+)-tetraconazole were 3.12, 3.76 days with washing procedure and 3.18, 4.05 days without washing procedure. The processing factors of strawberry wine samples after each step were generally less than 1. In particular, the processing factors of the fermentation process were the lowest. The results could help facilitate more accurate risk assessments of tetraconazole during wine-making process.
RESUMO
N-(2-trifluoromethyl-4-chlorophenyl)-2-oxocyclohexyl sulfonamide (chesulfamide) is in the limelight as a novel fungicide, and has fungicidal activity against Botrytis cinerea. For exploring more novel structures, 33 new compounds were synthesized by N-alkylation and acid-amine coupling reactions with chesulfamide as the core moiety, and their structures were characterized and established by ¹H-NMR, 13C-NMR, MS, and elemental analysis. The structure of (1R,2S)-2-(2-(N-(4-chloro-2-trifluoromethylphenyl)sulfamoyl)-cyclohexylamino)-N-(2-trifluoromethylphenyl) acetamide (II-19) was defined by X-ray single crystal diffraction. The in vivo and in vitro fungicidal activities against B. cinerea were evaluated. The bioassay results of mycelial growth demonstrated that most compounds exhibited excellent inhibitory activity against B. cinerea at 50 µg mL-1, and 7 compounds showed lower EC50 values than boscalid (EC50 = 4.46 µg mL-1) against B. cinerea (CY-09). In cucumber pot experiment, the inhibitory rates of four compounds (II-4, II-5, II-12, and II-13) against B. cinerea were 90.48, 93.45, 92.86, and 91.07, which were better than cyprodinil (88.69%), the best performing of all controls. In tomato pot experiment, the control efficacy of two analogs (II-8 and II-15) were 87.98 and 87.97% at 200 µg mL-1, which were significantly higher than boscalid (78.10%). Most compounds have an excellent fungicidal effect on B. cinerea, with potential as a lead compound for developing new pesticides.
Assuntos
Botrytis/efeitos dos fármacos , Fungicidas Industriais/síntese química , Fungicidas Industriais/farmacologia , Glicina/análogos & derivados , Sulfonamidas/síntese química , Sulfonamidas/farmacologia , Fungicidas Industriais/química , Glicina/síntese química , Glicina/química , Glicina/farmacologia , Relação Estrutura-Atividade , Sulfonamidas/químicaRESUMO
A series of novel 2-substituted aminocycloalkylsulfonamides were designed and synthesized by highly selective N-alkylation reaction, whose structures were characterized by 1H NMR, 13C NMR and HRMS. Among them, the configuration of compounds III12 and III20 were confirmed by X-ray single crystal diffraction. Bioassays demonstrated that the title compounds had considerable effects on different strains of Botrytis cinerea and Pyricularia grisea. Comparing with positive control procymidone (EC50=10.31mg/L), compounds III28, III29, III30 and III31 showed excellent fungicidal activity against a strain of B. cinerea (CY-09), with EC50 values of 3.17, 3.04, 2.54 and 1.99mg/L respectively. Their in vivo fungicidal activities were also better than the positive controls cyprodinil, procymidone, boscalid and carbendazim in pot experiments. Moreover, the fungicidal activity of III28 (EC50=4.62mg/L) against P. grisea was also better than that of the positive control isoprothiolane (EC50=6.11mg/L). Compound III28 would be great promise as a hit compound for further study based on the structure-activity relationship.