Fungistatic activity of Zanthoxylum rhoifolium Lam. bark extracts against fungal plant pathogens and investigation on mechanism of action in Botrytis cinerea

Plant-derived compounds are emerging as an alternative choice to synthetic fungicides. Chloroform–methanol extract, obtained from the bark of Zanthoxylum rhoifolium, a member of Rutaceae, showed a fungistatic effect on Botrytis cinerea, Sclerotinia sclerotiorum, Alternaria alternata, Colletotrichum gloeosporioides and Clonostachys rosea, when added to the growth medium at different concentrations. A fraction obtained by gel separation and containing the alkaloid O-Methylcapaurine showed significant fungistatic effect against B. cinerea and S. sclerotiorum, two of the most destructive phytopathogenic fungi. The underlying mechanism of such an inhibition was further investigated in B. cinerea, a fungus highly prone to develop fungicide resistance, by analysing the expression levels of a set of genes (BcatrB, P450, CYP51 and TOR). O-Methylcapaurine inhibited the expression of all the analysed genes. In particular, the expression of BcatrB gene, encoding a membrane drug transporter involved in the resistance to a wide range of xenobiotic compounds, was strongly inhibited (91%).     

超高效液相色谱-四极杆-飞行时间质谱法快速筛查农药制剂中非法添加的化学杀菌剂

建立了超高效液相色谱-四极杆-飞行时间质谱法(UPLC-Q-TOF MS)快速筛查农药制剂中35种非法添加化学杀菌剂的方法.农药制剂样品经甲醇超声溶解提取后,采用Zorbax C18色谱柱(100 mm×1.8 mm,2.1μm)进行分离,以0.1%甲酸-乙睛作为流动相进行梯度洗脱,采用正离子全扫描模式进行分析.在所建立的条件下,35种杀菌剂在0.2,0.4和2.0 mg/kg水平下的添加回收率为81.0%~101.3%,相对标准偏差为1.0%~4.4%.在100份样品有6份样品中筛查出添加了化学杀菌剂,并进行了含量分析.本方法分析效率高,结果准确可靠,适用于农药制剂中非法添加化学杀菌剂的定性筛查.     

基于共价有机骨架材料的磁固相萃取-超高效液相色谱-串联质谱法测定水中4种杀菌剂

杀菌剂在环境中长期富集后会引起土壤和植物病害,并能借助雨水或灌溉渗透到深层土壤和地下水中,威胁水体环境和人体健康。因此针对水中杀菌剂开发简单快速、高效灵敏的分析方法至关重要。该研究通过原位合成法制备了磁性共价有机骨架材料Fe₃O₄@TpBD,将其作为萃取吸附剂,富集环境水体中苯并咪唑杀菌剂(噻菌灵、麦穗宁、多菌灵)和有机硫杀菌剂(稻瘟灵)。利用Fe₃O₄@TpBD与杀菌剂之间的π-π共轭、氢键和静电作用进行吸附,结合超高效液相色谱-串联质谱法(UHPLC-MS/MS)进行检测,建立了测定水中4种痕量杀菌剂的分析方法。通过透射电子显微镜、X射线衍射及傅里叶变换红外光谱等方式对Fe₃O₄@TpBD进行表征,以证明材料的成功合成。对萃取条件进行一系列的优化(Fe₃O₄@TpBD的磁性比例及用量、水样pH、吸附时间、洗脱液的种类及体积、洗脱时间、NaCl含量),确定了最佳萃取条件。4种杀菌剂在3~1200 ng/L的范围内线性关系良好,线性相关系数均大于0.998,方法的检出限和定量限分别为0.06~0.28 ng/L和0.20~0.92 ng/L。在15、150和600 ng/L 3个加标水平下进行加标回收试验,日内和日间精密度分别为2.8%~10.0%和4.4%~15.7%。将该方法用于实际水样的检测,4种杀菌剂的加标回收率为77.1%~119.1%,在水库水中检测出多菌灵,含量为27.5 ng/L。该方法灵敏度高,准确度和精密度良好,操作简单,耗时短。     

Determination of strobilurin fungicide residues in fruits and vegetables by nonaqueous micellar electrokinetic capillary chromatography with indirect laser‐induced fluorescence

A nonaqueous micellar electrokinetic capillary chromatography method with indirect LIF was developed for the determination of strobilurin fungicide residues in fruits and vegetables. Hydrophobic CdTe quantum dots (QDs) synthesized in aqueous phase were used as background fluorescent substance. The BGE solution, QD concentration, and separation voltage were optimized to obtain the best separation efficiency and the highest signal intensity. The optimal BGE solution consists of 40 mM phosphate, 120 mM sodium dodecyl sulfate, 15% v/v water and 15% v/v hydrophobic CdTe QDs in formamide, of which apparent pH is 9.5. The optimized separation voltage is controlled as 25 kV. The resultant detection limits of azoxystrobin, kresoxim‐methyl, and pyraclostrobin are all 0.001 mg/kg, their linear dynamic ranges are 0.005–2.5 mg/kg, and the recoveries of the spiked samples are 81.7–96.1%, 86.5–95.7%, and 87.3–97.4%, respectively. This method has been proved to be sensitive enough to detect the aforementioned fungicides in fruits and vegetables at the maximum residue limits.     

Synthesis,crystal structure and antifungal activity of a divalent cobalt(II) complex with uniconazole

Azole compounds have attracted commercial interest due to their high bactericidal and plant‐growth‐regulating activities. Uniconazole [or 1‐(4‐chlorophenyl)‐4,4‐dimethyl‐2‐(1H‐1,2,4‐triazol‐1‐yl)pent‐1‐en‐3‐ol] is a highly active 1,2,4‐triazole fungicide and plant‐growth regulator with low toxicity. The pharmacological and toxicological properties of many drugs are modified by the formation of their metal complexes. Therefore, there is much interest in exploiting the coordination chemistry of triazole pesticides and their potential application in agriculture. However, reports of complexes of uniconazole are rare. A new cobalt(II) complex of uniconazole, namely dichloridotetrakis[1‐(4‐chlorophenyl)‐4,4‐dimethyl‐2‐(1H‐1,2,4‐triazol‐1‐yl‐κN⁴)pent‐1‐en‐3‐ol]cobalt(II), [CoCl₂(C₁₅H₁₈ClN₃O)₄], was synthesized and structurally characterized by element analysis, IR spectrometry and X‐ray single‐crystal diffraction. The crystal structural analysis shows that the Co^II atom is located on the inversion centre and is coordinated by four uniconazole and two chloride ligands, forming a distorted octahedral geometry. The hydroxy groups of an uniconazole ligands of adjacent molecules form hydrogen bonds with the axial chloride ligands, resulting in one‐dimensional chains parallel to the a axis. The complex was analysed for its antifungal activity by the mycelial growth rate method. It was revealed that the antifungal effect of the title complex is more pronounced than the effect of fungicide uniconazole for Botryosphaeria ribis, Wheat gibberellic and Grape anthracnose.     

Dynamic residual pattern of azoxystrobin in Swiss chard with contribution to safety evaluation

This study aimed at quantifying the residual amount of azoxystrobin in Swiss chard samples grown under greenhouse conditions at two different locations (Gwangju and Naju, Republic of Korea). Samples were extracted with acetonitrile, separated by salting out, and subjected to purification by using solid‐phase extraction. The analyte was identified using liquid chromatography–ultraviolet detection. The linearity of the calibration range was excellent with coefficient of determination 1.00. Recovery at three different spiking levels (0.1, 0.5, and 4 mg/kg) ranged between 82.89 and 109.46% with relative standard deviation <3. The limit of quantification, 0.01 mg/kg, was considerably much lower than the maximum residue limit (50 mg/kg) set by the Korean Ministry of Food and Drug Safety. The developed methodology was successfully used for field‐treated leaves, which were collected randomly at 0–14 days following azoxystrobin application. The rate of disappearance in/on Swiss chard was ascribed to first‐order kinetics with a half‐life of 8 and 5 days, in leaves grown in Gwangju and Naju greenhouses, respectively. Risk assessments revealed that the acceptable daily intake percentage is substantially below the risk level of consumption at day 0 (in both areas), thus encouraging its safe consumption.     

高效液相色谱–串联质谱法同时测定土壤中8种杀菌剂残留

建立高效液相色谱-串联质谱法同时测定土壤中戊唑醇、腈菌唑、腈苯唑、氟硅唑、三唑酮、丙环唑、烯唑醇、苯醚甲环唑8种杀菌剂残留量的方法。采用QuEChERS样品前处理方法对土壤样品进行提取、净化和富集,用电喷雾离子源、正负离子扫描,以多反应监测(MRM)模式进行定性和定量分析。在优化的实验条件下,8种杀菌剂的质量浓度在0.01~0.50 mg/L范围内与色谱峰面积均成良好的线性关系,相关系数均大于0.995,方法检出限为0.005~0.010 mg/kg。样品平均加标回收率为85.6%~102.2%,测定结果的相对标准偏差为4.6%~13.2%(n=5)。该方法操作简便,灵敏度和准确度高,满足土壤中戊唑醇等8种杀菌剂残留量的测定要求。     

Magnetic solid-phase extraction of Zineb by C18-functionalised paramagnetic nanoparticles and determination by first-derivative spectrophotometry

Fe₃O₄-SiO₂-C₁₈ paramagnetic nanoparticles have been synthesised and used as magnetic solid-phase extraction (MSPE) sorbent for the extraction of Zineb from agricultural aqueous samples under ultrasonic condition and quantified through a first-derivative spectrophotometric method. The produced magnetic nanoparticles were characterised by using scanning electron microscopy, X-ray diffraction spectroscopy, Fourier transform infrared spectroscopy and zeta potential reader. The Fe₃O₄-SiO₂-C₁₈ paramagnetic nanoparticles had spherical structures with diameters in the range of 198–201 nm. Further, MSPE was performed by dispersion of Fe₃O₄-SiO₂-C₁₈ paramagnetic nanoparticles in a buffered aqueous solution accompanied by sonication. Next, the sorbents were accumulated by applying an external magnetic field and were washed with 4-(2-pyridylazo) resorcinol-dimethyl sulfoxide solution, for the purpose of desorbing the analyte. The extraction conditions (sample pH, washing and elution solutions, amount of sorbents, time of extraction, sample volume and effect of diverse ions), as well as Zineb-PAR first-order derivative spectra, were also evaluated. The calibration curve of the method was linear in the concentration range of 0.055–24.3 mg L^?1 with a correlation coefficient of 0.991. The limit of detection and limit of quantification values were 0.022 and 0.055 mg L^?1, respectively. The precision of the method for 0.27 mg L^?1 solution of the analyte was found to be less than 3.2%. The recoveries of three different concentrations (0.27, 1.37 and 13.7 mg L^?1) obtained 98.3%, 98.5% and 96.0%, respectively. The proposed Fe₃O₄-SiO₂-C₁₈ paramagnetic nanoparticles were found to have the capability of reusing for 7.0 times.     

四硫代碳酸钠的合成及其生物活性

以元水Na2S,CS2和S为原料制备了四硫代碳酸钠。探讨了其物理、化学性质及生物活性。     

复合物Ⅲ抑制剂型杀菌剂——结构类型和作用机理*

复合物III是细胞呼吸链的重要组成部分,也是杀菌剂的重要作用靶标之一,近年来以复合物III为靶标的杀菌剂应用越来越广泛。本文在总结了复合物III结构和功能最新研究成果的基础上,系统综述了抗霉素A、氰霜唑、Surangin B等Q_i位点抑制剂,甲氧丙烯酸酯类、噁唑菌酮、粘噻唑、标桩菌素、UHDBT等Q_o位点抑制剂,以及双位点抑制剂NQNO与复合物III的作用机理,并对各类杀菌剂的构效关系进行了归纳和讨论。