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1.
Mikrochim Acta ; 189(1): 23, 2021 12 10.
Artigo em Inglês | MEDLINE | ID: mdl-34893943

RESUMO

A synthesis route of using cellulose as the precursor to prepare porous carbon (PC) had been established in this study. The as-prepared PC was introduced as carriers in the synthesis process of porous carbon-molecularly imprinted polymers (PC-MIPs), which greatly improved the absorption capacity of MIPs. Triazine pesticides in corn were extracted with matrix solid-phase dispersion (MSPD) using the PC-MIPs as dispersants and determined by ultraperformance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Under the optimal MSPD condition for extracting six kinds of triazines (simazine, terbutryn, simetryne, prometryne, ametryn, and atrazine), the detection limits were 0.005-0.02 ng g-1, while the precisions were 1.2-5.9%, and the recoveries were 92.6-104.7%. The method has been extensively applied to analyze various corn samples. Atrazine residue (1.2 µg kg-1) was detected in one corn sample, which was lower than the maximum residual limit indicated by the Chinese stated standards (50 µg kg-1).


Assuntos
Herbicidas/isolamento & purificação , Polímeros Molecularmente Impressos/química , Extração em Fase Sólida/métodos , Triazinas/isolamento & purificação , Zea mays/química , Adsorção , Carbono/química , Cromatografia Líquida de Alta Pressão , Herbicidas/análise , Herbicidas/química , Limite de Detecção , Porosidade , Espectrometria de Massas em Tandem , Triazinas/análise , Triazinas/química
2.
Molecules ; 26(21)2021 Nov 08.
Artigo em Inglês | MEDLINE | ID: mdl-34771155

RESUMO

The phytotoxicity and eco-compatibility of essential oils (EOs) from Eucalyptus gunnii (EG) and E. pulverulenta 'Baby Blue' (EP), cultivated in Italy for their cut foliage, were investigated. Leaf micromorphology, EOs phytochemical characterization, and phytotoxicity were analysed. EP revealed a significantly higher oil gland density and a higher EO yield with respect to EG. In both EOs, 1,8-cineole was the major compound (~75%), followed by α-pinene in EG (13.1%) and eugenol in EP (7.5%). EO phytotoxicity was tested on both weeds (Lolium multiflorum, Portulaca oleracea) and crops (Raphanus sativus, Lactuca sativa, Lepidium sativum, Solanum lycopersicum, Pisum sativum, Cucumis sativus). EG EO inhibited germination of P. oleracea, R. sativus, and S. lycopersicum seeds (ranging from 61.5 to 94.6% for the higher dose used), while affecting only radical elongation in S. lycopersicum (ranging from 66.7 to 82.6%). EP EO inhibited germination of P. oleracea and R. sativus (ranging from 41.3 to 74.7%) and affected radical elongation of L. sativum and L. multiflorum (ranging from 57.4 to 76.0%). None of the EOs affected the germination and radical growing of L. sativa, P. sativum, and C. sativus. Moreover, EP EO was more active than EG EO in inhibiting α-amylase, a key enzyme for seed growth regulation. Brine shrimp lethality assay showed that both EOs are safe for aquatic organisms, suggesting their high eco-compatibility. The data collected provide useful information for future applications of these EOs in agriculture as safe and selective bioherbicides.


Assuntos
Produtos Agrícolas/efeitos dos fármacos , Eucalyptus/química , Herbicidas/farmacologia , Óleos Voláteis/farmacologia , Compostos Fitoquímicos/farmacologia , Plantas Daninhas/efeitos dos fármacos , Animais , Artemia , Germinação/efeitos dos fármacos , Herbicidas/química , Herbicidas/isolamento & purificação , Óleos Voláteis/química , Óleos Voláteis/isolamento & purificação , Compostos Fitoquímicos/química , Compostos Fitoquímicos/isolamento & purificação
3.
Bioorg Chem ; 117: 105452, 2021 12.
Artigo em Inglês | MEDLINE | ID: mdl-34742026

RESUMO

Three pairs of undescribed enantiomeric α-pyrone derivatives (1a/1b-3a/3b) and six undescribed congeners (4-9), were obtained from the fungus Alternaria brassicicola that was isolated from the fresh leaves of Siegesbeckia pubescens Makino (Compositae). The structures of these new compounds were characterized by extensive NMR spectroscopic and HRESIMS data, and their absolute configurations were further elucidated by a modified Mosher's method, chemical conversion, single-crystal X-ray diffraction analysis, and ECD calculations. This is the first report of three pairs of enantiomeric α-pyrone derivatives from the fungus A. brassicicola, and these enantiomers were successfully acquired from scalemic mixtures via chiral HPLC. Compounds 1a/1b-3a/3b and 4-9 were evaluated for the herbicidal activity against Echinochloa crusgalli, Setaria viridis, Portulaca oleracea, and Taraxacum mongolicum. At a concentration of 100 µg/mL, compounds 1a and 1b could significantly inhibit the germination of monocotyledon weed seeds (E. crusgalli and S. viridis) with inhibitory ratios ranging from 68.6 ± 6.4% to 84.2 ± 5.1%, which was equivalent to that of the positive control (glyphosate). The potential structure-herbicidal activity relationship of these compounds was also discussed. To a certain extent, the results of this study will attract great interest for the potential practical application of promising fungal metabolites, α-pyrone derivatives, as ecofriendly herbicides.


Assuntos
Alternaria/química , Herbicidas/farmacologia , Pironas/farmacologia , Asteraceae/química , Relação Dose-Resposta a Droga , Echinochloa/efeitos dos fármacos , Herbicidas/química , Herbicidas/isolamento & purificação , Estrutura Molecular , Portulaca/efeitos dos fármacos , Pironas/química , Pironas/isolamento & purificação , Setaria (Planta)/efeitos dos fármacos , Relação Estrutura-Atividade , Taraxacum/efeitos dos fármacos
4.
Chem Biodivers ; 18(12): e2100679, 2021 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-34651409

RESUMO

Pomelo seeds (PS) are important by-product of pomelo fruits (Citrus grandis Osbeck). The value-added utilization of PS remains highly challenged. This study aimed to investigate the utilization potential of PS as natural antioxidant, antibacterial, herbicidal agents, and their functional components. The ethanolic extract (EE) of PS and its four fractions as PEE (petroleum ether extract), AcOEtE (ethyl acetate extract), BTE (butanol extract), and WE (water extract), were prepared and biologically evaluated. BTE exhibited the best antioxidant activity among all these extracts, in both ABTS (2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt) and FRAP (ferric reducing antioxidant power) assays. AcOEtE was superior to other extracts in herbicidal assay against both Festuca elata Keng (IC50 of 0.48 mg mL-1 ) and Amaranthus retroflexus L. (IC50 of 0.94 mg mL-1 ). Meanwhile, both AcOEtE and BTE demonstrated inhibitory effects against Bacillus subtilis, Escherichia coli, and Xanthomonas citri subsp. citri, with MIC ranging 2.5-5.0 mg mL-1 . Furthermore, the primary chemical components involving naringin, deacetylnomilin, limonin, nomilin, and obacunone, were quantified in all these extracts. PCA (principal component analysis) suggested that naringin might highly contribute to the antioxidant activity of PS, and the herbicidal activity should be ascribed to limonoids. This study successfully identified AcOEtE and BTE as naturally occurring antioxidant, antibacterial, and herbicidal agents, showing application potential in food and cosmetics industries, and organic farming agriculture.


Assuntos
Antibacterianos/farmacologia , Antioxidantes/farmacologia , Citrus/química , Herbicidas/farmacologia , Extratos Vegetais/farmacologia , Sementes/química , Amaranthus/efeitos dos fármacos , Antibacterianos/química , Antibacterianos/isolamento & purificação , Antioxidantes/química , Antioxidantes/isolamento & purificação , Bacillus subtilis/efeitos dos fármacos , Benzotiazóis/antagonistas & inibidores , Escherichia coli/efeitos dos fármacos , Festuca/efeitos dos fármacos , Herbicidas/química , Herbicidas/isolamento & purificação , Testes de Sensibilidade Microbiana , Extratos Vegetais/química , Extratos Vegetais/isolamento & purificação , Ácidos Sulfônicos/antagonistas & inibidores , Xanthomonas/efeitos dos fármacos
5.
Int J Mol Sci ; 22(18)2021 Sep 10.
Artigo em Inglês | MEDLINE | ID: mdl-34575982

RESUMO

Glyphosate is a highly effective, low-toxicity, broad-spectrum herbicide, which is extensively used in global agriculture to control weeds and vegetation. However, glyphosate has become a potential threat to human and ecosystem because of its excessive usage and its bio-concentration in soil and water. Herein, a novel turn-on fluorescent probe, N-n-butyl-4-(3-pyridin)ylmethylidenehydrazine-1,8-naphthalimide (NPA), is proposed. It efficiently detected Cu2+ within the limit of detection (LOD) of 0.21 µM and displayed a dramatic turn-off fluorescence response in CH3CN. NPA-Cu2+ complex was employed to selectively and sensitively monitor glyphosate concentrations in real samples accompanied by a fluorescence turn-on mode. A good linear relationship between NPA and Cu2+ of glyphosate was found in the range of 10-100 µM with an LOD of 1.87 µM. Glyphosate exhibited a stronger chelation with Cu2+ than NPA and the system released free NPA through competitive coordination. The proposed method demonstrates great potential in quantitatively detecting glyphosate in tap water, local water from Songhua River, soil, rice, millet, maize, soybean, mung bean, and milk with mild conditions, and is a simple procedure with obvious consequences and no need for large instruments or pretreatment.


Assuntos
Técnicas Biossensoriais , Glicina/análogos & derivados , Herbicidas/isolamento & purificação , Naftalimidas/química , Cobre/química , Corantes Fluorescentes/química , Glicina/química , Glicina/isolamento & purificação , Glicina/toxicidade , Herbicidas/química , Herbicidas/toxicidade , Humanos , Limite de Detecção , Pontos Quânticos/química , Rios/química , Poluentes do Solo/isolamento & purificação , Poluentes do Solo/toxicidade , Água/química , Poluentes da Água/isolamento & purificação , Poluentes da Água/toxicidade
6.
Molecules ; 26(15)2021 Jul 30.
Artigo em Inglês | MEDLINE | ID: mdl-34361785

RESUMO

Even today, weeds continue to be a considerable problem for agriculture. The application of synthetic herbicides produces serious environmental consequences, and crops suffer loss of their activity due to the appearance of new resistant weed biotypes. Our aim is to develop new effective natural herbicides that improve the problem of resistance and do not harm the environment. This work is focused on a bioassay-guided isolation and the characterization of natural products present in Moquiniastrum pulchrum leaves with phytotoxic activity and its preliminary application in weeds. Moquiniastrum pulchrum was selected for two reasons: it is an abundant species in the Cerrado region (the second most important ecosystem in Brazil, after the Amazon)-the explanation behind its being a dominant species is a major focus of interest-and it has traditional employment in folk medicine. Six major compounds were isolated in this plant: one flavone and five diterpenes, two of which are described for the first time in the literature. Four of the six compounds exhibited phytotoxic activity in the bioassays performed. The results confirmed the phytotoxic potential of this plant, which had not been investigated until now.


Assuntos
Asteraceae/química , Agentes de Controle Biológico/toxicidade , Diterpenos/toxicidade , Flavonas/toxicidade , Herbicidas/toxicidade , Plantas Daninhas/efeitos dos fármacos , Controle de Plantas Daninhas/métodos , Bioensaio , Agentes de Controle Biológico/química , Agentes de Controle Biológico/isolamento & purificação , Produtos Agrícolas/crescimento & desenvolvimento , Diterpenos/química , Diterpenos/isolamento & purificação , Flavonas/química , Flavonas/isolamento & purificação , Herbicidas/química , Herbicidas/isolamento & purificação , Humanos , Estrutura Molecular , Extratos Vegetais/química , Folhas de Planta/química , Plantas Daninhas/crescimento & desenvolvimento
7.
J Chromatogr A ; 1653: 462407, 2021 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-34315063

RESUMO

Efficient capture of strongly polar, ionizable and trace phenoxycarboxylic acids herbicides (PCAHs) from aqueous samples is essential and challenging for environmental monitoring. In the present work, electric field-assisted solid-phase microextraction (EFA-SPME) based on monolith/aminated graphene oxide composite was developed for the first time to efficiently extract trace PCAHs prior to HPLC-tandem mass spectrometry (HPLC-MS/MS) quantification. First, poly (1-allyl-3-methylimidazole difluoromethanesulfonylamide salt-co-divinylbenzene/ethylene dimethacrylate) monolith/aminated graphene oxide composite (MAC) was prepared on the surface of stainless steel wire and employed as the extraction phase of SPME. After that, the MAC-based fiber and a stainless steel wire were connected to a DC power supply that allowed the implement of variable electric fields during adsorption and desorption processes. Various key factors influencing the extraction performance were inspected in detailed. Results well evidenced that the exertion of electric fields improved the enrichment performance, accelerated the trap and release procedures. The proposed MAC/EFA-SPME-HPLC-MS/MS method achieved wide linear ranges (0.005-50.0 µg/L), low limits of detection (0.54-1.3 ng/L) and good precision (2.7-7.0%) for the quantification of PCAHs. The related extraction mechanism was deduced. Additional, the current approach was successfully applied to monitor studied PCAHs at trace contents in environment waters, and the accuracy was confirmed by confirmatory experiments.


Assuntos
Monitoramento Ambiental , Grafite , Herbicidas , Microextração em Fase Sólida , Cromatografia Líquida de Alta Pressão , Monitoramento Ambiental/métodos , Grafite/química , Herbicidas/análise , Herbicidas/isolamento & purificação , Espectrometria de Massas em Tandem
8.
J Chromatogr A ; 1651: 462339, 2021 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-34161838

RESUMO

A new sensitive and selective analytical methodology to quantify glyphosate (GLY), aminomethylphosphonic acid (AMPA), and glufosinate (GLU) in both soil and earthworms (Allolobophora chlorotica) was developed. The extraction and purification methods were optimized. The samples were extracted with various aqueous solutions (HNO3, H2O, KOH and borate buffer) and derivatized with 9-Fluorenylmethyl chloroformate (FMOCCl). To optimize the extraction step, a method to remove the excess FMOCCl was applied based on liquid-liquid extraction with diethyl ether. The purification of derivatized extracts was carried out using XLB solid phase extraction (SPE) cartridges before internal standard quantification by liquid chromatography coupled to tandem mass spectrometry (LC/MS/MS). The elution step was optimized to obtain the best recoveries possible, which was with acidic methanol (1% formic acid) (67% for GLY, 70% for GLU and 65% for AMPA). The extraction and purification method followed by analysis of the two herbicides and AMPA in soils using LC/MS/MS determined limit of quantification (LOQ) values of 0.030 µg g - 1 for GLY, 0.025 µg g - 1 for AMPA and 0.020 µg g - 1 for GLU . For earthworms, LOQ were 0.23 µg g - 1 for GLY, 0.20 µg g - 1 for AMPA and 0.12 µg g - 1 for GLU. . The developed method was applied to determine these compounds in natural soils and earthworms.


Assuntos
Aminobutiratos/análise , Técnicas de Química Analítica/métodos , Glicina/análogos & derivados , Oligoquetos/química , Organofosfonatos/análise , Solo/química , Aminobutiratos/isolamento & purificação , Animais , Técnicas de Química Analítica/instrumentação , Cromatografia Líquida , Glicina/análise , Glicina/isolamento & purificação , Herbicidas/análise , Herbicidas/isolamento & purificação , Organofosfonatos/isolamento & purificação , Extração em Fase Sólida , Espectrometria de Massas em Tandem
9.
J Chromatogr A ; 1651: 462321, 2021 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-34144398

RESUMO

A high-efficiency approach for the synthesis of molecularly imprinted polymers has been developed and further for the solid-phase extraction of sulfonylurea herbicides in food samples. Molecular simulation approach combined chemometric selected metsulfuron-methyl (MSM) and 2-trifluoromethyl acrylic acid (TFMAA) as the template and the monomer to synthesize the molecularly imprinted polymers (MIPs). Experimental validation confirmed that the MSM-imprinted polymers showed a higher selectivity and affinity to sulfonylurea herbicides. The optimized molecularly imprinted solid-phase extraction (MISPE) conditions, including loading, washing, and eluting conditions, were established. The developed MISPE technology combined HPLC-MSMS was successfully used for the determination of sulfonylurea herbicides in foods. Compared with commercial SPE columns, MISPE showed high affinity, excellent selectivity and low matrix effect. The recoveries of sulfonylurea herbicides spiked in four matrices were between 86.4% and 100.2%, with the relative standard deviations (RSD) in the range of 0.9%-10.5%.


Assuntos
Técnicas de Química Analítica/métodos , Herbicidas/isolamento & purificação , Polímeros Molecularmente Impressos/síntese química , Compostos de Sulfonilureia/isolamento & purificação , Sulfonatos de Arila/química , Cromatografia Líquida de Alta Pressão , Herbicidas/análise , Humanos , Extração em Fase Sólida , Compostos de Sulfonilureia/análise , Espectrometria de Massas em Tandem
10.
J Chromatogr A ; 1651: 462301, 2021 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-34107399

RESUMO

In this work, a core-shell structured magnetic covalent organic framework named as M-TpDAB was constructed with 3,3'-diaminobenzidine (DAB) and 1,3,5-triformylphloroglucinol (Tp) as building units. M-TpDAB was characterized by infrared spectroscopy, nitrogen adsorption-desorption isotherms, powder X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Using the M-TpDAB as adsorbent, a simple and highly effective method was proposed for preconcentrating phenylurea herbicides before high performance liquid-phase chromatography analysis. In the optimized conditions, a good linearity was achieved within the range of 0.15-100 ng mL-1 for water sample, 1.0-100.0 ng mL-1 for tea drink samples. The limits of detection for the analytes were 0.05-0.15 ng mL-1 for water sample and 0.30-0.50 ng mL-1 for drink samples. Satisfactory recoveries of spiked target compounds were in the range of 84.6%-105% for water sample and 80.3%-102% for tea drink samples. Finally, the M-TpDAB based method was successfully used to determine phenylurea herbicides in tea drinks and water samples, demonstrating a good alternative for analyzing trace level of phenylurea herbicides in water samples.


Assuntos
Herbicidas/isolamento & purificação , Estruturas Metalorgânicas/química , Compostos de Fenilureia/isolamento & purificação , Extração em Fase Sólida/métodos , Água/química , Adsorção , Cromatografia Líquida de Alta Pressão , Água Potável/química , Herbicidas/análise , Fenômenos Magnéticos , Magnetismo/métodos , Compostos de Fenilureia/análise , Difração de Raios X
11.
Biosci Biotechnol Biochem ; 85(7): 1602-1608, 2021 Jun 24.
Artigo em Inglês | MEDLINE | ID: mdl-34003212

RESUMO

The use of biopesticides has expanded rapidly in recent years; however, their use in weed control is less advanced. Herein, we describe the development of a weed control agent by screening 208 plant extracts (104 species) for their plant growth-inhibition activities, which resulted in 142 active samples (from 89 plant species). Verbascoside, isolated from the shoots of Verbena incompta, was identified as a growth inhibitor against rice root (EC50, 1.75 m m), and its root growth-inhibition activity was also confirmed in radish, tomato, and Lotus japonicus. Verbascoside is composed of hydroxytyrosol (EC50,12.51 m m) and caffeic acid (EC50, 4.08 m m), 2 poorly water-soluble phenolic components with weak growth-inhibition activities, and 2 sugars, which are more soluble but inactive. The plant apparently developed a more active and highly soluble compound by condensing these 4 components. We conclude that a biopesticide containing verbascoside may be useful for weed-control purposes.


Assuntos
Glucosídeos/farmacologia , Herbicidas/farmacologia , Fenóis/farmacologia , Raízes de Plantas/efeitos dos fármacos , Verbena/química , Glucosídeos/química , Glucosídeos/isolamento & purificação , Herbicidas/isolamento & purificação , Fenóis/química , Fenóis/isolamento & purificação , Raízes de Plantas/crescimento & desenvolvimento , Plantas Daninhas/efeitos dos fármacos , Plantas Daninhas/crescimento & desenvolvimento , Análise Espectral/métodos
12.
J Chromatogr A ; 1649: 462188, 2021 Jul 19.
Artigo em Inglês | MEDLINE | ID: mdl-34034108

RESUMO

A new green method for trace level quantification of four herbicides, glyphosate (GLYP), glufosinate (GLUF), and their main metabolites, aminomethylphosphonic acid (AMPA) and 3-(methyl-phosphinico)-propionic acid (MPPA), was developed. The purification step without any derivatization was conducted by solid-phase extraction using Chelex-100 resin in the Fe (III) form, followed by elution with 5% NH4OH. The four analytes were quantified by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry. The developed extraction method was validated on five fresh and sea water matrices with mean recoveries ranging from 80.1% to 109.4% (relative standard deviation < 20%). The extraction conditions were evaluated and certified for the high applicability of the extraction method too. The limits of detection (ng/L) in the five water matrices were in ranges 0.70 - 4.0, 2.4 - 3.9, 1.8 - 4.7, and 1.6 - 4.0 for GLYP, AMPA, GLUF, and MPPA, respectively. The method was successfully applied to detect the four compounds in surface waters sampled along the Red River Delta region in July 2019. The highest concentrations were detected at 565, 1,330, 234, and 871 ng/L for GLYP, AMPA, GLUF, and MPPA, respectively. These results showed the potential capacity of this new method for convenient monitoring of herbicides and their metabolites in the diverse natural water system.


Assuntos
Aminobutiratos/isolamento & purificação , Glicina/análogos & derivados , Organofosfonatos/isolamento & purificação , Extração em Fase Sólida/métodos , Poluentes Químicos da Água/isolamento & purificação , Aminobutiratos/análise , Cromatografia Líquida de Alta Pressão , Água Doce/química , Glicina/análise , Glicina/isolamento & purificação , Herbicidas/análise , Herbicidas/isolamento & purificação , Organofosfonatos/análise , Espectrometria de Massas em Tandem , Poluentes Químicos da Água/análise
13.
J Chromatogr A ; 1647: 462143, 2021 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-33957346

RESUMO

Molecularly imprinting polymers with high selectivity toward 29 sulfonylurea herbicides were synthesized by precipitation polymerization, using metsulfuron-methyl and chlorsulfuron as the template molecule, 4-vinylpyridine as the function monomer, divinylbenzene as the crosslinking agent, and acetonitrile as porogen. The imprinted polymers were characterized and measured by scanning electron microscopy (SEM) and equilibrium adsorption experiments. The molecularly imprinted polymers displayed specific recognition for the tested 29 sulfonylurea herbicides, and the maximum apparent binding capacity was found to be 18.81 mg/g. The synthesized polymer was used as a solid-phase extraction (SPE) column coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) for determination of the tested analytes in agro-products. Within the range of 2-100 µg/L, the tested analytes have achieved a good linear association with correlation coefficient (R2) > 0.999. The calculated limits of detection (LODs, S/N=3) as along with limits of quantification (LOQs, S/N=10) were in the ranges of 0.005-0.07 µg/L and 0.018-0.23 µg/L, respectively. Under different spiking levels, the recovery rates were ranged from 74.8% - 110.5%, and the relative standard deviation (RSDs) were < 5.3%. Finally, the feasibility of the proposed methodology was successfully applied for detection of sulfonylurea herbicides in crops, vegetables, and oils samples.


Assuntos
Herbicidas , Impressão Molecular/métodos , Polímeros Molecularmente Impressos/química , Extração em Fase Sólida/métodos , Compostos de Sulfonilureia , Agricultura , Cromatografia Líquida , Herbicidas/análise , Herbicidas/química , Herbicidas/isolamento & purificação , Limite de Detecção , Modelos Lineares , Reprodutibilidade dos Testes , Compostos de Sulfonilureia/análise , Compostos de Sulfonilureia/química , Compostos de Sulfonilureia/isolamento & purificação , Espectrometria de Massas em Tandem
14.
Artigo em Inglês | MEDLINE | ID: mdl-33957354

RESUMO

A novel in-syringe temperature-controlled liquid-liquid microextraction based on solidified floating ionic liquid (in-syringe TC-LLME-SFIL) combined with high performance liquid chromatography was developed for the simultaneous determination of monuron, chlorotoluron, atrazine, monolinuron, propazine and prometryn in commercial vegetable protein drinks. The samples were deproteinized by trichloroacetic acid and further cleaned up by solid phase extraction column. The ionic liquid tributyldodecylphosphonium tetrafluoroborate ([P4 4 4 12]BF4) was used as extraction solvent and dispersed into the depurated sample solution to form fine droplets with the assistance of heating and vortex. With the help of an ice bath, the ionic liquid phase solidified and floated on the surface of aqueous phase. After separation from the aqueous phase, the solidified ionic liquids were dissolved with acetonitrile and the resulting solution was analyzed by high performance liquid chromatography. Some extraction parameters, including type and amount of adsorbent, type and amount of ionic liquids, amount of NaCl, melting temperature and time of ionic liquid, vortex time, pH of sample solution, ice bath temperature and time, were investigated and optimized by single-factor experiment, Plackett-Burman design and Box-Behnken design. The results showed that good linearities (r ≥ 0.9994) were obtained in the concentration range of 7.8-1000.0 µg/L. The limits of detection and quantification were in the range of 0.25-2.59 µg/L and 0.82-8.63 µg/L, respectively. The spiked recoveries were 81.26-118.42% with the relative standard deviation (RSD, n = 3) lower than 8.17%. The present method was successfully applied to the simultaneous determination of triazine and phenylurea herbicides in vegetable protein drinks.


Assuntos
Sucos de Frutas e Vegetais/análise , Microextração em Fase Líquida , Resíduos de Praguicidas , Compostos de Fenilureia , Triazinas , Cromatografia Líquida de Alta Pressão/métodos , Herbicidas/análise , Herbicidas/isolamento & purificação , Líquidos Iônicos/química , Limite de Detecção , Modelos Lineares , Microextração em Fase Líquida/instrumentação , Microextração em Fase Líquida/métodos , Resíduos de Praguicidas/análise , Resíduos de Praguicidas/isolamento & purificação , Compostos de Fenilureia/análise , Compostos de Fenilureia/isolamento & purificação , Proteínas de Vegetais Comestíveis/análise , Reprodutibilidade dos Testes , Seringas , Triazinas/análise , Triazinas/isolamento & purificação
15.
Artigo em Inglês | MEDLINE | ID: mdl-33865541

RESUMO

The genotoxic and cytotoxic effects of 2,4-dichlorophenoxyacetic acid (2,4-D) on specimens of Astyanax lacustris were evaluated using different biomarkers. Additionally, this study evaluated the efficiency of an activated carbon filter made from the husks green coconut, which was used as a biosorbent to remove 2,4-D dissolved in the water, and the potential effectiveness of this procedure for the reduction of the toxic effects of this compound on A. lacustris. Three sublethal concentrations of 2,4-D (10, 20, and 40 mg L-1) were tested over 24, 48, and 72 h, and their effects on Astyanax lacustris were evaluated using chromosomal aberration test, the mitotic index, the frequency of micronuclei and nuclear alterations, and the comet assay. Exposure to 2,4-D increased the frequency of chromosomal aberrations, reduced the mitotic index, and caused significant levels of nuclear modification in some of the treatments, in comparison with the negative control. The comet assay revealed DNA damage (classes 1-3) at all 2,4-D concentrations, reaching significant levels in the 20 mg L-1 (48 h) and 40 mg L-1 (72 h) treatments. The coconut husk biosorbent was highly effective for the removal of 2,4-D and the fish exposed to the water decontaminated by this filter had low levels of cellular alteration. The findings of the present study demonstrated, for the first time, the genotoxic and cytotoxic effects of 2,4-D in Astyanax lacustris, as well as suggests the potential application of a biosorbent for the effective decontamination of water contaminated with pesticides.


Assuntos
Ácido 2,4-Diclorofenoxiacético/isolamento & purificação , Ácido 2,4-Diclorofenoxiacético/toxicidade , Materiais Biocompatíveis/farmacocinética , Characidae , Recuperação e Remediação Ambiental/métodos , Absorção Fisico-Química/efeitos dos fármacos , Animais , Materiais Biocompatíveis/química , Characidae/genética , Aberrações Cromossômicas/induzido quimicamente , Aberrações Cromossômicas/veterinária , Cocos/química , Ensaio Cometa , Análise Citogenética/veterinária , Dano ao DNA , Monitoramento Ambiental/métodos , Filtração/instrumentação , Filtração/métodos , Herbicidas/isolamento & purificação , Herbicidas/toxicidade , Testes de Mutagenicidade , Poluentes Químicos da Água/isolamento & purificação , Poluentes Químicos da Água/toxicidade , Purificação da Água/métodos
16.
Carbohydr Polym ; 262: 117906, 2021 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-33838794

RESUMO

Silver nanoparticle (AgNP) incorporated chitosan-Polyvinyl alcohol (Ch/PVA) hydrogel nanocomposite was fabricated by repeated freeze-thaw treatment using glutaraldehyde as crosslinker for removal of herbicide butachlor from aqueous solution. Ch/PVA hydrogel provided a matrix for in-situ immobilization of AgNPs and were characterized by various physicochemical techniques. AgNPs of size 5-20 nm possessed crystalline structure, led to increase in thermal stability and surface area after incorporation into Ch/PVA hydrogel. Ch/PVA hydrogel nanocomposite showed maximum adsorption of butachlor (86.55 %) at 30 °C and pH 3.0, while Ch/PVA-Ag showed a slight increase in adsorption of butachlor following pseudo-second order kinetics. Langmuir and Freundlich models with different error functions (R2, R2adj, RSME, χ2 and RSS), confirmed monolayer adsorption of butachlor.


Assuntos
Acetanilidas/isolamento & purificação , Quitosana/química , Nanopartículas Metálicas/química , Nanocompostos/química , Álcool de Polivinil/química , Prata/química , Adsorção , Reagentes de Ligações Cruzadas/química , Glutaral/química , Herbicidas/isolamento & purificação , Humanos , Cinética , Espectroscopia de Infravermelho com Transformada de Fourier/métodos , Temperatura
17.
Molecules ; 25(16)2020 Aug 11.
Artigo em Inglês | MEDLINE | ID: mdl-32796576

RESUMO

Dicamba is a moderately volatile herbicide used for post-emergent control of broadleaf weeds in corn, soybean, and a number of other crops. With increased use of dicamba due to the release of dicamba-resistant cotton and soybean varieties, growing controversy over the effects of spray drift and volatilization on non-target crops has increased the need for quantifying dicamba collected from water and air sampling. Therefore, this study was designed to evaluate stable isotope-based direct quantification of dicamba from air and water samples using single-quadrupole liquid chromatography-mass spectrometry (LC-MS). The sample preparation protocols developed in this study utilize a simple solid-phase extraction (SPE) protocol for water samples and a single-step concentration protocol for air samples. The LC-MS detection method achieves sensitive detection of dicamba based on selected ion monitoring (SIM) of precursor and fragment ions and relies on the use of an isotopically labeled internal standard (IS) (D3-dicamba), which allows for calculating recoveries and quantification using a relative response factor (RRF). Analyte recoveries of 106-128% from water and 88-124% from air were attained, with limits of detection (LODs) of 0.1 ng mL-1 and 1 ng mL-1, respectively. The LC-MS detection method does not require sample pretreatment such as ion-pairing or derivatization to achieve sensitivity. Moreover, this study reveals matrix effects associated with sorbent resin used in air sample collection and demonstrates how the use of an isotopically labeled IS with RRF-based analysis can account for ion suppression. The LC-MS method is easily transferrable and offers a robust alternative to methods relying on more expensive tandem LC-MS/MS-based options.


Assuntos
Cromatografia Líquida/métodos , Dicamba/análise , Herbicidas/análise , Marcação por Isótopo/métodos , Extração em Fase Sólida/métodos , Espectrometria de Massas em Tandem/métodos , Água/química , Ar , Dicamba/isolamento & purificação , Herbicidas/isolamento & purificação , Limite de Detecção
18.
J Chromatogr A ; 1626: 461362, 2020 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-32797841

RESUMO

Exploring new material as adsorbent for the efficient enrichment of pollutants is always of great significance in analytical chemistry. In this work, a magnetic azobenzene framework (labeled as MAzo) was constructed as a magnetic solid phase extraction (MSPE) adsorbent by a simple and environmentally benign strategy. The MAzo exhibited the attractive features of strong magnetism, outstanding adsorption performance, as well as good reusability. Combining MAzo-based MSPE with high performance liquid-phase chromatography, a simple and effective method was developed for simultaneous determination of four phenylurea herbicides in pear juice and apple juice samples. Under optimized experimental conditions, the method offered low limits of detection of 0.05-0.15 ng mL-1, high recoveries of 86.7-109.2% with RSD less than 7%. Density functional theory calculation indicated that the good adsorption performance of MAzo for PUHs can be ascribed to the strong H-bonding forces and weak π-π interactions. The facile, green, low-cost synthesis method together with the excellent adsorption performance endows the MAzo great application prospect in sample preparation.


Assuntos
Compostos Azo/química , Poluentes Ambientais/análise , Herbicidas/análise , Compostos de Fenilureia/análise , Extração em Fase Sólida/métodos , Adsorção , Cromatografia Líquida de Alta Pressão , Poluentes Ambientais/isolamento & purificação , Sucos de Frutas e Vegetais/análise , Herbicidas/isolamento & purificação , Fenômenos Magnéticos , Malus , Estruturas Metalorgânicas , Compostos de Fenilureia/isolamento & purificação , Pyrus
19.
J Chromatogr A ; 1628: 461438, 2020 Sep 27.
Artigo em Inglês | MEDLINE | ID: mdl-32822978

RESUMO

A fast, simple, environmentally friendly and sensitive on-line concentration method using microemulsion system as background solution (BGS) was developed for the trace detection of propazine, atrazine, simazine in food samples. The electrokinetic injection assisted micelle to cyclodextrin stacking (MCDS) was designed for the enrichment of target compounds. The factors affected enrichment performance, such as the kind of CDs, the amount of CDs, the concentration of methanol in BGS, the concentration of micelle in sample matrix, the concentration of phosphoric acid in BGS and the sample injection time were optimized. The optimized electrophoretic condition was obtained as following: 50 mM α-CD, 20 mM SDS in sample matrix., 80 mM PA and 20% MeOH (v/v) in BGS, sample solution by electrokinetic injection at -10 kV for 80 s. Under the optimized conditions described above, the linear range was 0.1-20 ug/mL with a good linear relationship with a correlation coefficient (r) ≥ 0.9985. The SEFs for the propazine, atrazine, simazine were found to be 123, 85 and 62 respectively. The proposed MCDS-MEEKC method provided an efficient method for trace analysis of triazine herbicides in honey and dendrobium officinale samples.


Assuntos
Técnicas de Química Analítica/métodos , Cromatografia Capilar Eletrocinética Micelar , Ciclodextrinas/química , Herbicidas/isolamento & purificação , Micelas , Triazinas/isolamento & purificação , Atrazina , Ácidos Fosfóricos , Simazina
20.
Chem Biodivers ; 17(9): e2000407, 2020 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-32634284

RESUMO

We aimed to evaluate the bioherbicide potential of Eucalyptus saligna leaf litter essential oil, its fractions and major compounds. Six essential oil fractions were obtained by preparative thin-layer chromatography and analyzed by gas chromatography/mass spectrometry. Effects of the oil, its fractions and major compounds (1,8-cineole and/or α-pinene) diluted in aqueous solution were assessed on germination and seedling growth. Recipient species were Lactuca sativa (model), Amaranthus viridis (weed), Eragrostis plana (weed), and Paspalum notatum (forage). The essential oil was more phytotoxic on A. viridis and L. sativa, followed by E. plana, and caused no effects on P. notatum. Amaranthus viridis was inhibited by all treatments, mainly the essential oil, α-pinene and fraction 6, whereas E. plana was more affected by the oil fractions. Results revealed the species-specific phytotoxic effects of E. saligna essential oil, indicating its potential use for controlling A. viridis and E. plana. Phytotoxic effects of essential oils or their components should not be generalized, as effects may change according to recipient species.


Assuntos
Amaranthus/efeitos dos fármacos , Eragrostis/efeitos dos fármacos , Eucalyptus/química , Herbicidas/farmacologia , Óleos Voláteis/farmacologia , Folhas de Planta/química , Herbicidas/química , Herbicidas/isolamento & purificação , Óleos Voláteis/química , Óleos Voláteis/isolamento & purificação , Controle de Plantas Daninhas
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