Study on Tonghaosu and Its Analogs： Isolation, Structure Identification and Synthesis of Antifeedant B-ring-homo-tonghaosu

The methanolic extract from a Chinese endemic Chrysanthemum plant, Dendranthema indicum var. aromaticum, was found to show high antifeeding activity against Pieris brassicae L., and by bioassay-guided separation, the active component, B-ring-homo-tonghaosu, 2-(2‘,4‘-hexadiynylidene)-1,6-dioxaspiro-[4,5]-dec-3-ene (2) was isolated. Its structure was elucidated by comparing its spectroscopic data with those of 2 reported in the literatures. Furthermore new convenient total synthesis methods of B-ring-homo-tonghaosu were also developed to confirm its structure and make its further application in crop protection available. In addition, extensive comparison of spectroscopic data showed that the structure of compound 21 reported in literature should be revised to 2.     

^31P NMR对马拉硫磷乳油中马拉硫磷及其有机磷杂质的分析

采用31P NMR对马拉硫磷乳油中马拉硫磷及主要有机磷杂质进行分析,确定了马拉硫磷及4个主要有机磷杂质的含量.实验测定马拉硫磷乳油中马拉硫磷、O,O,S-三甲基二硫代磷酸酯、O,O,O-三甲基硫代磷酸酯、异马拉硫磷及马拉氧磷的含量分别是44.92%,0.55%,0.05%,0.22%,0.11%,相对标准偏差分别为0.07%,2.10%,2.88%,0.94%,1.58%.分析结果表明,31P NMR是测定马拉硫磷及其有机磷杂质的含量的有效方法,解决了农药分析的实际问题,具有很好的实用性.     

Synthesis,Crystal Structure and Biological Activities of N-Octyl Rotenone Oximino Carbamate

The title compound N-octyl rotenone oximino carbamate(C32H40N2O7) has been synthesized by the reaction of rotenone oxime with octyl isocyanate,and its crystal structure was determined by single-crystal X-ray diffraction.The crystal belongs to the monoclinic system,space group P21 with a=11.4311(8),b=10.3717(7),c=12.7490(9),β=105.0770(10)°,Z=2,V=1459.49(18)3,Mr=564.66,Dc=1.285g/cm3,S=1.087,μ=0.090 mm-1,F(000)=604,the final R=0.0426 and wR=0.0937 for 2599 observed reflections(I2σ(I)).X-ray analysis reveals that the molecule has an approximately V-shaped structure,and the absolute configurations of C(7),C(8) and C(18) are R,S and R,respectively.The oxime ester is in an E configuration.Intermolecular N-H…O hydrogen bond exists in the crystal.The preliminary bioassay shows that the title compound possesses strong insecticidal activity against Mythimna separate,and displays moderate fungicidal activity against Erysiphe graminis.     

色氨酸、半胱氨酸和酪氨酸的高效毛细管电泳分析

用自组装的高效毛细管电泳安培检测装置,对具有常规电活性的色氨酸,半胱氨酸和酪氨酸进行了分离分析条件的研究,采用重力进样方式,进样高度25cm,进样时间15S,在分离毛细管长70cm,内径25um,的电泳装置上,10mmol/L K2HPO4-H3PO4缓冲液（PH10．5）,20KV分离高压,＋1．05V（vs SCE)检测电位的条件下,对酸解毛发中得到的混合氨基酸中的色氨酸,半胱氨酸和酪氨酸进行了分离测定,结果令人满意。     

噻吩N-芳基吡唑类化合物的合成及光活化活性研究

以2,6-二氯-4-三氟甲基苯胺和溴代噻吩等为起始原料,设计并合成了12个未见报道的噻吩芳基吡唑类化合物5a～51,经1H NMR,13C NMR,ESI-MS和元素分析对化合物的结构进行了表征.初步生物活性测定结果表明,目标化合物均具有一定的光活化杀虫活性,其中51表现最为明显.在光照下对白纹伊蚊幼虫的LC50值为0.04 μg/mL,达到了商品化品种氟虫腈的水平.     

毛细管电泳安培法检测酚类化合物

使用自行设计组装的毛细管电泳柱端安培检测系统 ,对四个酚类化合物进行了分离检测。研究了工作电极、缓冲液及其 p H值、检测电压和分离电压对分离检测的影响。在优化条件下 ,4个酚在 5× 1 0 -6～ 5× 1 0 -4 mol/L范围内峰高与浓度成良好的线性关系 ,检测下限为 8.5× 1 0 -7mol/L     

小麦中多种农药的快速残留分析

建立了同时测定小麦中12种农药(灭线磷、甲拌磷、甲基毒死蜱、八氯二丙醚、马拉硫磷、毒死蜱、氟虫腈、杀扑磷、溴虫腈、三唑磷、联苯菊酯和甲氰菊酯)残留的快速分析方法.样品采用改进的QuEChERS进行前处理,用1%乙酸乙腈提取,C18和中性氧化铝双重净化后,结合GC-MS/SIM对小麦中的12种农药进行检测.结果表明,小麦中12种农药的加标水平为0.025 ～1.0 mg/kg时,平均回收率为76% ～108%,相对标准偏差为0.4% ～10.5%;方法的定量下限(S/N=10)为0.5 ～9.8 μg/kg,低于欧盟设定的MRLs值.     

新型茼蒿素类似物的合成和抗虫构效关系研究

Twenty-one tonghaosu analogs were synthesized via hydroamination or selective reduction of the endocyclic double bond of the corresponding dienol spiroketals. Structures of all the new compounds were confirmed by ^1H NMR, IR, MS, HREIMS or elemental analysis. Their antifeedant activity against large white butterfly （Pieris brassicae L） and larvicidal activity toward mosquito （Culex quinquefasciatus Say） were examined. Some of them exhibited antifeeding activities comparable to or stronger than tonghaosu Z-1. Based on the activity data, the preliminary structure-activity relationship was also discussed, which might be instructive for finding out lead compounds with better bioactivities in the future.     

31P NMR对马拉硫磷乳油中马拉硫磷及其有机磷杂质的分析

采用³¹P NMR对马拉硫磷乳油中马拉硫磷及主要有机磷杂质进行分析,确定了马拉硫磷及4个主要有机磷杂质的含量. 实验测定马拉硫磷乳油中马拉硫磷、O,O,S-三甲基二硫代磷酸酯、O,O,O-三甲基硫代磷酸酯、异马拉硫磷及马拉氧磷的含量分别是44.92%,0.55%,0.05%,0.22%,0.11%,相对标准偏差分别为0.07%,2.10%,2.88%,0.94%,1.58%. 分析结果表明,³¹P NMR是测定马拉硫磷及其有机磷杂质的含量的有效方法,解决了农药分析的实际问题,具有很好的实用性.     

新型含氟嘧啶胺类衍生物的合成及其抑菌活性

以盐酸胍和丙二酸二乙酯为起始原料,经环合、羟基氯代、三氟乙氧基化等反应合成了10个新型的含氟嘧啶胺类衍生物,结构经1H NMR,IR和GC-MS表征。初步的抑菌活性测试结果表明:用药量为100 mg.L-1时,2-氨基-4,6-二(2,2,2-三氟乙氧基)嘧啶和N-(2,6-二氯苄基)-2-氨基-4-氯-6-(2,2,2-三氟乙氧基)嘧啶对马铃薯早疫病和烟草炭疽病有较好的抑菌活性。