Pyrethroids and terrestrial non-target organisms

The discovery and development of the pyrethroid insecticides represents a major advance in the techniques of crop protection and disease vector control. These compounds combine outstanding efficacy against a broad spectrum of noxious insects with low toxicity to birds and mammals. This paper considers the effects of pyrethroids on other components of the terrestrial non-target fauna, with particular reference to effects on ‘beneficial’ organisms, including natural pest-control agents, pollinators, and organisms responsible for the maintenance of soil structure and fertility. This paper uses laboratory and field data to identify which groups of organisms may be potentially at risk from the use of pyrethroids, and draws on extensive field data to consider the significance of such hazards under conditions of normal use. Emphasis will be placed throughout on the evaluation of these compounds under practical conditions, including both crop and non-crop usages. Limitations to, and opportunities for, the use of pyrethroids are discussed, and the potential for further development is considered.     

Towards the rational design of crop protection agents

The crop protection industry has consistently provided new and improved products during the past forty years. The discovery process has, to a large extent, relied upon empirical procedures and imitative chemistry to generate these compounds. Although these methods will continue to be employed, it is envisaged that additional technology will be incorporated into the process and in this respect the development of molecular biology, computational sciences and biophysical techniques is discussed. The successful integration of these skills requires an open and communicative environment involving multi-disciplinary research groups.     

Influence of chlorine substituents on biological activity of chemicals: a review

A number of well known polychlorinated chemicals are toxicologically and environmentally unsafe. Because of their persistence they are in the focus of public discussions against chlorine chemistry. However, chlorinated organic chemicals in the molecular weight range between 200 and 600 constitute an important and indispensable segment in the arsenal of existing biologically active chemicals used as pharmaceuticals or crop‐protection agents. Over the course of time it has been found empirically that the introduction of a chlorine atom into one or more specific positions of a biologically active molecule may substantially improve the intrinsic biological activity. In some cases the presence of a chlorine atom is crucial for significant activity in compounds derived both from nature and chemical synthesis. But in other cases chlorination diminishes or abolishes biological activity, as shown for chlordane homologues. Thus a chlorine atom, like any other substituent, is a modulator of activity. Almost all non‐reactive chlorinated chemicals and chlorine‐free chemicals are devoid of any biological activity at the highest concentration typically used in primary screening tests for discovery of useful biological properties. The influence of a substituent such as chlorine on the biological activity of a potential drug or crop protection agent still has to be established empirically in biological experiments designed to detect desired activity or toxicological properties. Sometimes chlorine does prove to be the optimum for improvement of activity. Long‐term rigorous investigations of several hundred chlorinated compounds, registered by the authorities as pharmaceutical drugs or crop‐protection agents, show that the generalisation ‘all chlorinated chemicals are dangerous’, deduced from the negative toxicological properties of a hundred chlorinated and reactive compounds of low molecular weight that are relevant in terms of safe working conditions in the chemical industry and for ecological safety, is not justified. Chlorinated compounds are not necessarily toxic or dangerous. Highly reactive chemicals or polychlorinated compounds cannot be compared with regard to toxicological properties with unreactive compounds having a low degree of chlorination. The chlorine atom, as one of many possible substituents used in synthetic organic chemistry, will remain in the future one of the important tools for probing structure–activity relationships in life science research and as a molecular component in commercialised compounds, in order to provide safer, more selective and more environmentally compatible products with higher activity for medicine and agriculture. © 1999 WILEY‐VCH Verlag GmbH     

Natural products that have been used commercially as crop protection agents

Many compounds derived from living organisms have found a use in crop protection. These compounds have formed the basis of chemical synthesis programmes to derive new chemical products; they have been used to identify new biochemical modes of action that can be exploited by industry-led discovery programmes; some have been used as starting materials for semi-synthetic derivatives; and many have been used or continue to be used directly as crop protection agents. This review examines only those compounds derived from living organisms that are currently used as pesticides. Plant growth regulators and semiochemicals have been excluded from the review, as have living organisms that exert their effects by the production of biologically active secondary metabolites.     

Natural products in plant protection

Natural products can be used to control pests and diseases in crops. These products include anorganic compounds, but also a variety of plant extracts. In the beginning of this century active microbial extracts were discovered as well. Synthetic crop protection chemicals were developed from about 1940 onwards and sustained progress in modern agriculture. The first generation chemicals have aspecific modes of toxic action and are in many instances deleterious to the environment. The second generation chemicals have specific modes of action and meet modern environmental requirements. A disadvantage of these chemicals is the potency of target organisms to acquire resistance. This condition urged agrochemical industry to develop chemicals with new modes of action. Such chemicals can be developed by using natural bioactive products as leads in synthesis programmes. This paper decribes the progress that was made in the development of natural bioactive compounds in pest and disease control.     

Dung‐inhabiting fungi: a potential reservoir of novel secondary metabolites for the control of plant pathogens

Coprophilous fungi are a large group of saprotrophic fungi mostly found in herbivore dung. The number of these fungi undergoing investigation is continually increasing, and new species and genera continue to be described. Dung‐inhabiting fungi play an important ecological role in decomposing and recycling nutrients from animal dung. They produce a large array of bioactive secondary metabolites and have a potent enzymatic arsenal able to utilise even complex molecules. Bioactive secondary metabolites are actively involved in interaction with and defence against other organisms whose growth can be inhibited, resulting in an enhanced ecological fitness of producer strains. Currently, these antibiotics and bioactive secondary metabolites are of interest in medicine in particular, while very little information is available concerning their potential use in agriculture. This review introduces the ecology of dung‐inhabiting fungi, with particular emphasis on the production of antibiotic compounds as a means to compete with other microorganisms. Owing to the fast pace of technological progress, new approaches to predicting the biosynthesis of bioactive metabolites are proposed. Coprophilous fungi should be considered as elite candidate organisms for the discovery of novel antifungal compounds, above all in view of their exploitation for crop protection. © 2015 Society of Chemical Industry     

土壤中苯肽胺酸的测定及淋溶特性研究

建立了反相条件下超高效液相色谱-串联质谱(UPLC-MS/MS)检测土壤中苯肽胺酸残留量的分析方法,并结合土壤薄层层析试验研究了苯肽胺酸在3种典型土壤(黑土、水稻土和红土)中的淋溶特性。结果表明:添加水平为0.1、1和10 mg/kg时,苯肽胺酸在土壤中的添加回收率为77.3%~99.4%,相对标准偏差(RSD)为1.3%~11.4%;其在3种土壤中的检出限(LOD)均低于1.0μg/kg。苯肽胺酸在吉林黑土中的比移值(Rf)为0.83,其移动性为可移动;在江苏水稻土中的Rf值为0.61,在湖南红土中的Rf值为0.62,移动性均为中等。     

新型杀菌剂苯菌酮在3种典型土壤中的淋溶行为

农药在土壤中的淋溶规律已成为研究热点之一,同时也是农药登记的必备数据。建立了土壤中苯菌酮残留量的超高效液相色谱-串联质谱(UPLC-MS/MS)分析方法,并通过土壤薄层层析和土柱淋溶试验,研究了苯菌酮在我国3种典型土壤中的淋溶行为。结果表明:苯菌酮在3种土壤中的平均添加回收率在81%~109%之间,相对标准偏差(RSD)为1.2%~13.4%,检出限(LOD)为0.29~0.30μg/kg。薄层层析试验表明,苯菌酮在河北潮土、湖南红壤和黑龙江黑土中的比移值(Rf)分别为0.17、0.26和0.15。土柱淋溶试验表明,苯菌酮在河北潮土、湖南红壤及黑龙江黑土第1段(0~10 cm)土柱中的含量比例(R1)分别为原始添加量的99%、80%和99%。根据我国化学农药环境安全评价标准,苯菌酮在3种土壤中的迁移特性均为不易移动,因此不易对地下水造成污染。研究结果可为苯菌酮在我国登记以及其安全使用提供基础数据。     

Stability of the tranquilizer drug propionylpromazine hydrochloride in formulated products

An analytical method to evaluate propionylpromazine hydrochloride (PPZHCl) in tranquilizer formulations was developed using high-performance liquid chromatography (HPLC). During analysis of aged quality-control samples, a previously unreported chromatographic response was observed at a shorter retention time than PPZHCl. Further investigation of formulations stored in trap tap devices at temperatures ranging from 5 to 40 degrees C during field trials at four different locations confirmed the degradation of the active ingredient. Further investigation using HPLC/tandem mass spectrometry revealed two to five degradates, with the major degradates being oxidation products of the active ingredient, PPZHCl. As PPZHCl formulations must be stable when stored at 5 to 40 degrees C for 6 to 12 months, reformulation with the anti-oxidant ascorbic acid was utilized to achieve the required PPZHCl stability.     

Natural products in plant protection

Natural products can be used to control pests and diseases in crops. These products include anorganic compounds, but also a variety of plant extracts. In the beginning of this century active microbial extracts were discovered as well. Synthetic crop protection chemicals were developed from about 1940 onwards and sustained progress in modern agriculture. The first generation chemicals have aspecific modes of toxic action and are in many instances deleterious to the environment. The second generation chemicals have specific modes of action and meet modern environmental requirements. A disadvantage of these chemicals is the potency of target organisms to acquire resistance. This condition urged agrochemical industry to develop chemicals with new modes of action. Such chemicals can be developed by using natural bioactive products as leads in synthesis programmes.This paper decribes the progress that was made in the development of natural bioactive compounds in pest and disease control.     

UPLC-MS/MS法检测稻米及土壤中扑草净除草剂的残留量

建立检测稻米及土壤中扑草净的UPLC-MS/MS方法。稻米和土壤样品经乙腈和混合液提取,甲醇/二氯甲烷溶解,PSA固相萃取柱净化,氮气吹干后经UPLC-MS/MS测定,外标法定量。建立了水稻及土壤中提取扑草净残留量的液相色谱-质谱/质谱测定方法。扑草净在稻米及土壤中的最低检测质量分数分别为0.01mg/kg;最小检出量5×10~11g;稻米添加回收率为82.7%~105.3%,土壤中添加回收率为79.6%~103.3%;稻米的RSD为2.6%~3.6%,土壤的RSD为3.2%~5.2%。建立方法准确、快速、灵敏度高,能够满足扑草净残留量分析的要求。     

农用抗生素的筛选策略

微生物是具有农用生物活性的代谢产物的重要来源。本文将就筛选策略对近年来从微生物中筛选具有农用生物活性代谢产物即农用抗茸素所取得的进展进行综述，其中包括分离新的或稀有微生物类群、发酵技术的改进、建立新的筛选模型及高通量筛选技术及色谱-光谱联用技术等方面。新的微生物类群是产生新的具有农用生物活性的代谢产物的重要目标；发酵技术的改进将会提高新的代谢产物出现的机会和检测的机率；新的筛选模型的创建和改进有助于发现新的代谢产物；高通量筛选技术有助于提高筛选的速度;而色谱-光谱联用技术的运用将避免不必要的重复工作，加快化合物的早期鉴别速度。     

合成生物学助力链霉菌天然产物农药创制与产业化

病虫草害防控是国家总体安全建设的重要组成部分。微生物天然产物农药是病虫草害绿色防控体系的重要成员, 在保障国家粮食安全、生态安全和农产品质量安全, 筑牢国家生物安全屏障中具有重要作用。链霉菌以能够产生丰富的次级代谢产物而著称, 是天然产物农药的资源宝库, 也是重要的天然产物药物的工业生产菌。然而, 随着病虫草害抗药性增强, 新发、突发病虫草害增多等问题不断涌现, 以及天然产物研究面临新骨架、高活性化合物发现难度增大, 工业菌株产量提升困难等瓶颈, 链霉菌天然产物农药创制与应用正面临巨大挑战。合成生物学作为一门交叉学科, 突破了生物学研究的传统模式, 为天然产物药物研发提供了新的思路与策略。本文综述了近年来合成生物学在链霉菌研究领域的技术革新, 以及合成生物学在推动链霉菌天然产物资源发现、天然产物高效生物制造等方面的研究进展, 并对合成生物学助力链霉菌天然产物农药的创制与产业化进行了展望。     

Diaryloxyacetate herbicides

The discovery and investigation of a novel family of herbicides containing a diaryl acetal are described. The stability of the acetal limited herbicidal efficacy and recognizing that fact led to the design of analogs with commercial levels of post-emergence activity on broadleaf weeds. These compounds inhibited acetolactate synthase and in vitro activity data were used to guide target design. However, no members of this family provided a commercially valuable combination of herbicidal efficacy and crop selectivity.     

植保无人飞机低空低容量喷雾技术应用与展望

近十年来,我国植保无人飞机迅猛发展,应用的农作物范围越来越广,不仅在水稻、小麦、玉米等主要粮食作物得到了应用,在橡胶、槟榔等高大植株的病虫害防治中更有其独特优势,已经初步形成了我国植保无人飞机低空低容量喷雾的喷头配置、配套药剂、飞防助剂、作业参数等技术体系,对于重要农作物病虫害如稻纵卷叶螟、水稻纹枯病、小麦蚜虫、玉米黏虫等防治效果均在80%以上,在各地病虫害防控中发挥了重要作用。但是,植保无人飞机喷雾作业过程中,还存在炸机或失控、雾滴飘移药害、药液分层结块、防治效果不稳定等问题。通过汇总分析植保无人飞机在重要病虫草害防治工作的成功经验和安全事故,本文提出植保无人飞机低容量喷雾技术将会得到更广泛的应用,植保无人飞机专用药剂和配套助剂、变量施药、多传感器数据融合、多机协同、精准施药、施药标准和规范等都将得到长足的发展,为现代农业和智慧农业发展提供技术支持。     

Conclusions from the workshop on evaluation and regulation of biological control agents

This paper reports on the Workshop on Evaluation and Regulation of Biological Control Agents (BCAs) held in Budapest on the 23–24 November 2015. Conclusions and recommendations are summarized and explained, and some of the ways in which the recommendations are being taken forward by the joint EPPO IOBC Panel on Biological Control are described. The key conclusions are that properly authorized releases of BCAs are beneficial for crop protection and the environment, with little evidence of adverse effects. Different countries apply different types of regulation in different ways to determine whether such releases can be authorized. A more harmonized approach could increase opportunities for use of biological control and ensure that potential risks are addressed in a more coherent and consistent way.     

QuEChERS-超高效液相色谱-串联质谱法测定玉米植株和土壤中溴氰虫酰胺及其代谢物残留

建立了超高效液相色谱-串联质谱 (UPLC-MS/MS) 测定玉米植株和土壤中溴氰虫酰胺及其代谢物J9Z38残留量的方法,明确了种子处理方式下两种化合物的消解动力学。样品经乙腈提取,采用QuEChERS方法处理后,进UPLC-MS/MS检测分析。结果表明:在0.01、0.1和1 mg/kg添加水平下,溴氰虫酰胺和J9Z38在玉米植株和土壤中的平均回收率在81%~103%之间,相对标准偏差均小于10.1%;在0.1~50 μg/L范围内,溴氰虫酰胺和J9Z38的质量浓度与相应峰面积间线性关系良好 (R2 > 0.999),定量限 (LOQ) 均为0.01 mg/kg。溴氰虫酰胺和J9Z38在玉米植株和土壤中的消解动态符合一级动力学模型,溴氰虫酰胺在玉米植株和土壤中的消解半衰期分别为8.3和8.2 d (春季),3.9和4.5 d (夏季)。该方法简单、灵敏、高效,能够满足溴氰虫酰胺及其代谢物J9Z38在玉米植株和土壤中残留的检测需求。     

对羟基苯基丙酮酸双氧化酶抑制剂筛选方法研究进展

对羟基苯基丙酮酸双氧化酶(HPPD)是植物体正常生长所必需的质体醌和生育酚生物合成路径中的关键酶,已成为当前最重要的除草剂作用靶标之一。发展快速、可靠的HPPD抑制剂筛选方法对研究小分子化合物与HPPD之间的相互作用,以及开展基于靶酶结构的新型HPPD抑制剂设计均具有重要意义。结合HPPD的结构和功能,文章从生物分析的角度分别就高效液相色谱、同位素标记、偶联法、电化学及简易筛选模型等方法在HPPD抑制剂筛选中的运用进行了总结,并对发展HPPD抑制剂的高通量筛选方法进行了展望。     

QuEChERS-液相色谱-串联质谱法检测糙米中氟唑环菌胺的残留

采用QuEChERS前处理与液相色谱-串联质谱 (LC-MS/MS) 技术,建立了糙米中氟唑环菌胺残留的分析方法。样品采用V(乙腈) : V(水)=80 : 20混合溶液涡旋提取,经PSA分散固相萃取净化,LC-MS/MS测定,外标法定量。结果表明:在0.001~0.1 mg/L范围内,氟唑环菌胺的质量浓度与对应的峰面积间线性关系良好,R2 > 0.996。在0.004、0.01和0.1 mg/kg添加水平下,氟唑环菌胺在糙米中的回收率为83%~95%,相对标准偏差 (RSD) 为3.9%~12%。以最小添加浓度确定氟唑环菌胺在糙米中的定量限 (LOQ) 为0.004 mg/kg,远低于国际食品法典委员会规定的最大残留限量 (MRL) 0.01 mg/kg。所建方法操作简单、准确度和灵敏度高,可用于糙米中氟唑环菌胺残留的检测。对中国6个省 (市) 40个糙米样品进行检测,氟唑环菌胺的残留量均低于LOQ 0.004 mg/kg。膳食风险评估结果表明,氟唑环菌胺目前在中国水稻上使用对一般人群的的健康风险很低。     

QuEChERS-超高效液相色谱-串联质谱法测定果蔬中螺虫乙酯、丁醚脲及代谢物残留

建立了QuEChERS前处理-超高效液相色谱-串联质谱 (UPLC-MS/MS) 测定果蔬中螺虫乙酯、丁醚脲及其6种代谢物 (螺虫乙酯-烯醇、螺虫乙酯-烯醇-糖苷、螺虫乙酯-单羟基、螺虫乙酯-酮-羟基、丁醚脲-脲和丁醚脲-甲酰胺) 残留量的分析方法。样品经破壁机匀浆,V(乙腈) : V(甲酸)=10 : 1混合溶液涡旋提取,定制的QuEChERS净化管净化,岛津Shim-pack XR-ODS色谱柱分离 (75 mm × 2.0 mm,1.6 μm)。采用电喷雾离子源正离子多反应监测模式进行质谱检测,外标法定量。丁醚脲-脲和丁醚脲-甲酰胺在0.001~0.1 mg/L范围内线性关系良好,其他6种化合物在0.005~0.5 mg/L范围内线性关系良好,R2 ≥ 0.999 3。验证了梨、葡萄、西瓜、芥蓝、芹菜和韭菜6种基质下方法的准确度和精密度,在0.001~0.5 mg/kg添加水平下,8种化合物的平均回收率在68%~94%之间,相对标准偏差在5.4%~15%之间,定量限为0.001~0.005 mg/kg。该方法简便、快速、可靠,适用于同时测定果蔬中上述8种化合物残留。