新型单取代苯磺酰内脲衍生物的合成及表征

以2-氯-5-氯甲基吡啶和不同取代基的苯磺酰氯为原料, 合成了7个新型的苯磺酰内脲类衍生物, 并用FT-IR, 1H NMR, 13C NMR, 元素分析对其结构进行了表征, 同时对合成目标化合物的反应条件进行了探究.     

Graphene‐coated fiber for solid‐phase microextraction of triazine herbicides in water samples

Graphene is a novel and interesting carbon material that could be used for the separation and purification of some chemical compounds. In this investigation, graphene was used as a novel fiber‐coating material for the solid‐phase microextraction (SPME) of four triazine herbicides (atrazine, prometon, ametryn and prometryn) in water samples. The main parameters that affect the extraction and desorption efficiencies, such as the extraction time, stirring rate, salt addition, desorption solvent and desorption time, were investigated and optimized. The optimized SPME by graphene‐coated fiber coupled with high‐performance liquid chromatography‐diode array detection (HPLC‐DAD) was successfully applied for the determination of the four triazine herbicides in water samples. The linearity of the method was in the range from 0.5 to 200 ng/mL, with the correlation coefficients (r) ranging from 0.9989 to 0.9998. The limits of detection of the method were 0.05‐0.2 ng/mL. The relative standard deviations varied from 3.5 to 4.9% (n=5). The recoveries of the triazine herbicides from water samples at spiking levels of 20.0 and 50.0 ng/mL were in the range between 86.0 and 94.6%. Compared with two commercial fibers (CW/TPR, 50 μm; PDMS/DVB, 60 μm), the graphene‐coated fiber showed higher extraction efficiency.     

Membrane protected conductive polymer as micro‐SPE device for the determination of triazine herbicides in aquatic media

A micro‐SPE technique was developed by fabricating a rather small package including a polypropylene membrane shield containing the appropriate sorbent. The package was used for the extraction of some triazine herbicides from aqueous samples. Solvent desorption was subsequently performed in a microvial and an aliquot of extractant was injected into GC‐MS. Various sorbents including aniline‐ortho‐phenylene diamine copolymer, newly synthesized, polypyrrole, multiwall carbon nanotube, C18 and charcoal were examined as extracting media. Among them, conductive polymers exhibited better performance. Influential parameters including extraction and desorption time, desorption solvent and the ionic strength were optimized. The developed method proved to be rather convenient and offers sufficient sensitivity and good reproducibility. The detection limits of the method under optimized conditions were in the range of 0.01–0.04 ng/mL. The RSDs at a concentration level of 0.1 ng/mL were obtained between 4.5 and 9.3% (n=5). The calibration curves of analytes showed linearity in the range of 0.05–10 ng/mL. The developed method was successfully applied to the extraction of selected triazines from real water samples. The whole procedure showed to be conveniently applicable and quite easy to manipulate.     

N-(5 -溴-4 -取代嘧啶-2 -基)苯磺酰脲化合物的合成和生物活性

乙酰羟基酸合成酶(Acetohydroxyacid synthase, AHAS, EC 4.1.3.18)是植物和微生物中亮氨酸、异亮氨酸和缬氨酸合成途径的一个关键酶, 以AHAS为靶标的磺酰脲类除草剂具有高效、高选择性和对环境友好的特点. 通过2-氨基-4-甲基嘧啶溴代反应以及进一步的衍生、磺酰基异氰酸酯的胺解, 合成了一系列含有5-溴嘧啶基的新磺酰脲. 其结构经¹H NMR、质谱和元素分析确定. 生物活性测试表明目标化合物在离体水平对大肠杆菌乙酰羟基酸合成酶同工酶AHASII表现出了与市售除草剂苯磺隆相当甚至更优的抑制活性, 而盆栽除草活性低于苯磺隆.     

Insight into herbicide resistance of W574L mutant Arabidopsis thaliana acetohydroxyacid synthase:molecular dynamics simulations and binding free energy calculations

Acetohydroxyacid synthase(AHAS) is the target enzyme of several classes of herbicides,such as sulfonylureas and imidazolinones.Now many mutant AHASs with herbicide resistance have emerged along with extensive use of herbicides,therefore it is imperative to understand the detailed interaction mechanism and resistance mechanism so as to develop new potent inhibitors for wild-type or resistant AHAS.With the aid of available crystal structures of the Arabidopsis thaliana(At) AHAS-inhibitor complex,molecular dyn...     

Determination of diphenylether herbicides in water samples by solid-phase microextraction coupled to liquid chromatography

Solid-phase microextraction (SPME) coupled to LC for the analysis of five diphenylether herbicides (aclonifen, bifenox, fluoroglycofen-ethyl, oxyfluorfen, and lactofen) is described. Various parameters of extraction of analytes onto the fiber (such as type of fiber, extraction time and temperature, pH, impact of salt and organic solute) and desorption from the fiber in the desorption chamber prior to separation (such as type and composition of desorption solvent, desorption mode, soaking time, and flush-out time) were studied and optimized. Four commercially available SPME fibers were studied. PDMS/divinylbenzene (PDMS/DVB, 60 microm) and carbowax/ templated resin (CW/TPR, 50 microm) fibers were selected due to better extraction efficiencies. Repeatability (RSD, < 7%), correlation coefficient (> 0.994), and detection limit (0.33-1.74 and 0.22-1.94 ng/mL, respectively, for PDMS/DVB and CW/TPR) were investigated. Relative recovery (81-104% for PDMS/DVB and 83-100% for CW/TPR fiber) values have also been calculated. The developed method was successfully applied to the analysis of river water and water collected from a vegetable garden.     

Comparative Study for the Removal of Oxadiazon from Aqueous Solutions by Adsorption on Chitosan and Activated Carbon

Abstract

In the present investigation, chitosan and activated carbon are used as adsorbents for the removal of oxadiazon from aqueous solutions. The analyzing system was a gas chromatograph equipped with mass selective detector. The equilibrium studies are systematically carried out in a batch process, covering various process parameters that include agitation time, adsorbent dosage, and pH of the aqueous solution. Also, the relationship between extraction of oxadiazon and volume of aqueous/organic phase as well as the effect of inorganic salt were investigated. Adsorption behavior was found to follow Freundlich and Langmuir isotherms. The adsorption mechanism is described by a pseudo-second-order kinetics.     

Towards the D1 Protein Application for the Development of Sensors Specific for Herbicides

Abstract

One of the most widespread groups of pesticides are the triazine herbicides. These substances inhibit photosynthesis by blocking electron transport in plant chloroplasts. The possibility of the chloroplast D1 protein application for determination of the herbicide concentration in solution was investigated. Potentiometry and cyclic voltammetry have been selected to monitor specific interaction between the D1 protein and herbicide. It was found that membranes with well-defined structure, like Langmuir-Blongett film are more suitable for sensitive sensor construction than cross-linked membranes. After addition of atrazine, the current through these multilayers appeared to increase 5 fold. The effect was found to be fast and irreversible. It has been proposed that the toxic action of herbicides on chloroplasts, traditionally interpreted by inhibition of electron flow along the chloroplast membrane, may also be the result of the thylakoid membrane depolarization.     

Design, synthesis and bioactivity of novel ALS inhibitors (V)——Initial model of the herbicidal sulfonylureas and fused heterocyclic sulfonamides binding with receptor

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Analysing half-lives for pesticide dissipation in plants

Overall dissipation of pesticides from plants is frequently measured, but the contribution of individual loss processes is largely unknown. We use a pesticide fate model for the quantification of dissipation by processes other than degradation. The model was parameterised using field studies. Scenarios were established for Copenhagen/Denmark and Shanghai/PR China, and calibrated with measured results. The simulated dissipation rates of 42 pesticides were then compared with measured overall dissipation from field studies using tomato and wheat. The difference between measured overall dissipation and calculated dissipation by non-degradative processes should ideally be contributable to degradation in plants. In 11% of the cases, calculated dissipation was above the measured dissipation. For the remaining cases, the non-explained dissipation ranged from 30% to 83%, depending on crop type, plant part and scenario. Accordingly, degradation is the most relevant dissipation process for these 42 pesticides, followed by growth dilution. Volatilisation was less relevant, which can be explained by the design of plant protection agents. Uptake of active compound from soil into plants leads to a negative dissipation process (i.e. a gain) that is difficult to quantify because it depends largely on interception, precipitation and plant stage. This process is particularly relevant for soluble compounds.