典型手性农药的光解研究

文章以汞灯为光源,在对映体水平上考察了六种典型手性农药的光化学降解。丙溴磷、马拉硫磷、稻丰散、三唑酮和甲氰菊酯等五种农药含有1个手性中心,存在两个对映体,对各对映体分别进行光解,结果表明光解速率基本一致,且几种手性农药是手性稳定的,未发现对映体转化现象,几种农药中有机磷农药降解较快,而甲氰菊酯降解最慢,半衰期长达280h。氯氰菊酯含有3个手性中心,存在4个可在非手性硅胶柱上得到拆分的异构体,每个异构体又存在两个对映体,因此共8个对映体。进一步对氯氰菊酯的一个反式异构体所含的一个单一对映体进行光解,结果发现存在一定的异构体转化,氯氰菊酯的另外3个异构体均有生成,按氯氰菊酯各异构体总量计算的光解半衰期为66.7h。     

新烟碱类农药呋虫胺对映体选择性研究进展

农业生产中,呋虫胺以外消旋体的形式销售和使用,在进入生态环境后出现对映体选择性降解、吸收、代谢、排泄等.不区分对映体间差异的传统风险评估给呋虫胺的合理使用与生态安全带来了诸多隐患.研究指出S-呋虫胺既是高毒体也是高活体,其生态毒性为R-呋虫胺的13.9~145.9倍,但R-呋虫胺也表现出较高的杀虫活性,且作物中优先降解,开发高比例的R体农药有利于维持杀虫活性的同时降低对非靶生物和生态环境的负效应.本文旨在综述呋虫胺对映体选择性生物活性、生态毒性及环境行为研究进展,为其科学难题的解决提供新思路,也为其科学有效管理提供理论依据.     

手性农药丁氟螨酯对斑马鱼胚胎的选择性发育毒性

近年来丁氟螨酯（CYF）对非靶标生物的发育毒性已成为一个值得关注的问题,但其对水生生物的对映选择性效应尚不清晰.为评估丁氟螨酯对斑马鱼胚胎的对映选择性毒性,通过96 h的暴露试验,研究了梯度浓度的丁氟螨酯消旋体及对映体对斑马鱼胚胎的急性毒性.此外,试验还研究了丁氟螨酯对斑马鱼胚胎孵化率、卵黄囊水肿、心包囊水肿和身体弯曲的影响.根据急性毒性结果可知,毒性大小为S-CYF > Rac-CYF > R-CYF,其中S-CYF的毒性是R-CYF的2.3倍.72 hpf,500 mg·L^-1的S-CYF可显著诱导胚胎产生卵黄囊水肿（YSE）、体轴弯曲（CB）等畸形效应（p<0.05）,而Rac-CYF降低了斑马鱼胚胎的孵化成功率.在本研究中发育毒性效应结果与急性毒性结果一致,均为S-CYF > Rac-CYF > R-CYF,表明丁氟螨酯对斑马鱼胚胎存在显著的对映选择性发育毒性,研究结果为丁氟螨酯的环境风险评估提供了理论依据.     

异丙甲草胺及其S型对映体对蚯蚓的急性毒性差异

采用OECD标准滤纸接触法、人工土壤法及自然土壤法研究了异丙甲草胺及其S型对映体对蚯蚓的急性致死作用及手性差异.结果表明,3种方法相比较,滤纸染毒法结果置信区间最大,可靠性较差.自然土壤中Rac-异丙甲草胺及S-异丙甲草胺对蚯蚓的急性毒性大于人工土壤;根据毒性分级,Rac-异丙甲草胺及其S型对映体均属于低毒级农药;3种试验方法所得的Rac-异丙甲草胺及S-异丙甲草胺对蚯蚓的LC50差别不大,表明这2种农药对蚯蚓急性毒性的手性差异较小.     

植物源杀虫剂川楝素对环境生物安全性评价

评价农药对环境中非靶标生物的毒性是新农药开发应用的重要环节.依据国家环境保护局"化学农药环境安全评价试验准则",测定了78%川楝素原粉和0.5%川楝素乳油对生态环境中非靶标生物的毒性,并进行了安全性评价.结果表明,川楝素原粉对鹌鹑、家蚕、蜜蜂、蚯蚓、瓢虫、蝌蚪等非靶标生物均为低毒;川楝素乳油对家蚕、蜜蜂、蚯蚓、瓢虫等均为低毒,对家蚕的生长发育具有一定的影响,对鹌鹑中毒,对蝌蚪高毒.可见,植物源杀虫剂川楝素对环境非靶标生物毒性低、较为安全,但在水田及桑园应慎用0.5%川楝素乳油.     

基于万古霉素手性柱的马来酸扑尔敏对映体分离及其识别机理

药物是环境介质中一类新型污染物,多数药物具有手性对映体特性,药物对映体的分离分析是研究对映体水平药物环境行为和效应的前提.采用商品手性柱Chirobiotic#x00AE;V,在反相条件下,对马来酸扑尔敏进行了手性分离,考察了不同流速、柱温、pH值和流动相组成对分离的影响,并优化了色谱条件.结果表明:以含0.1%(体积分数)冰醋酸和0.1%(体积分数)三乙胺的水溶液(TEAA)与四氢呋喃(THF)混合为流动相,在所研究范围内,随着流动相中THF含量的增加、pH值增大和流速增大,马来酸扑尔敏对映体的分离效果降低;柱温影响存在峰值现象,即分离效果随温度的升高先增大后减小.优化得到的拆分条件为:流动相TEAA∶THF为95∶5(V/V),pH值为3,流速为0.3 mL·min~(-1),柱温为15℃.利用分子对接技术模拟万古霉素不同区域与扑尔敏对映体间的相互作用,计算得到了最稳定结合能,据此预测对映体的出峰顺序与实验结果完全一致.初步手性识别机理研究结果表明,引起手性识别的主要作用力为氢键作用.     

四溴乙基环己烷(TBECH)立体异构体的分析方法与环境行为及毒性效应研究进展

1,2-二溴-4-（1,2-二溴乙基）-环己烷,又名TBECH（tetrabromoethylcyclohexane,四溴乙基环己烷）,是一种添加型的新型溴代阻燃剂.TBECH的立体结构复杂,具有4个异构体,每个异构体又均含有一对对映体.随着传统溴代阻燃剂的禁止生产或限制使用,TBECH作为替代品之一被广泛用于建筑业、纺织业和电子等各行业.TBECH具有长距离迁移性、生物累积性和潜在毒性,被认为是一种可能的持久性有机污染物.通过对TBECH立体异构体的分析方法、环境行为和毒性效应研究的最新进展进行综述发现,TBECH的检测通常采用气相色谱质谱联用法,但仅集中于对环境样品中TBECH非对映异构体的分离分析,对映体水平的检测将成为未来TBECH立体异构体分析的发展方向.TBECH已在大气、水体、沉积物、土壤等环境介质和生物体中被陆续检出,并对生物体产生内分泌干扰、生殖发育等毒性效应,其各立体异构体具有特异的环境行为,表现出选择性的生物累积、转化和毒性效应.鉴于目前TBECH环境行为的研究主要关注水生生态系统,而从立体异构体水平出发的研究还很欠缺,建议今后加强对陆生生态系统中TBECH污染状况、分布特征以及环境行为的研究,进一步从异构体和对映体水平深入探讨TBECH的环境过程和生物效应,全面认识环境中TBECH的迁移转化规律及最终归趋.      

快速城市化区域表层土壤中杀虫剂的空间分布及风险评估

为探讨快速城市化区域杀虫剂的分布特征,19种被忽视的杀虫剂,即苯基吡唑类(氟虫腈)、氯丹、硫丹、九氯、六氯苯、七氯、狄氏剂、艾氏剂、异狄氏剂、甲氧滴滴涕及其代谢产物被用来分析在珠江三角洲(珠三角)及其周边区域229个土壤样品中的浓度水平和空间分布.结果表明,高浓度的杀虫剂主要集中在珠三角中心地区,而低浓度的杀虫剂则分布在珠三角周边区域,这个分布模式与国民生产总值和人口密度的分布相似,表明社会经济因素对杀虫剂的分布有一定的影响.此外,在城市化发展进程中,土地使用类型的转变也可能会导致原城镇农耕地变成现城市居民区,从而使得禁用农药在珠三角中心区域浓度高.来源分析表明在珠三角及其周边区域土壤存在工业氯丹的新输入源.氟虫腈由于半衰期比较短,在很大部分的土壤样品中转化成了氟虫腈砜和氟虫腈硫醚.对土壤中19种杀虫剂进行人体风险评估发现,6个在高人口密度区域收集的样品对人体有潜在的致癌或非致癌风险.因此这些被忽视的杀虫剂在将来环境研究中需要引起关注.     

1,2,5,6-四溴环辛烷(TBCO)的分析方法、环境行为及毒性效应研究进展

1,2,5,6-四溴环辛烷（1,2,5,6-Tetrabromocyclooctane,TBCO）与六溴环十二烷（HBCD）同属于脂环族溴代阻燃剂.随着HBCD的禁止生产和限制使用,TBCO成为潜在的替代品,其生态和环境效应开始受到关注.通过对TBCO的性质、分析方法、环境行为和毒性效应研究进行综述,结果表明:TBCO具有2个非对映异构体（简称为异构体）,分别为α-TBCO和β-TBCO,其中β-TBCO有一对对映体;TBCO的检测一般采用气相色谱-质谱联用法;TBCO目前已在空气、土壤、沉积物及生物中检出,并显示出生物蓄积性、生物毒性以及异构体特异性的生物降解.需要指出的是,关于环境介质、生物体中TBCO的有限研究主要集中于水生生态系统,在陆生生态系统中的生物富集、食物链放大及毒性效应的研究非常匮乏.TBCO是否具有环境持久性和长距离传输能力尚存争议.建议全面开展TBCO的环境界面迁移行为、生物富集、代谢与毒性效应研究,特别是在陆生生态系统中的研究,并从异构体和对映体水平深入探讨,以期全面评价TBCO的生态和健康风险.      

六溴环十二烷对映体对玉米的生理和基因损伤研究

采用高效液相色谱法对α-六溴环十二烷(α-HBCD)对映体进行手性拆分,制备获得(+)-和(-)-对映体.以玉米为受试植物,利用水培实验方法,采用不同浓度梯度的(+)α-HBCD、(-)α-HBCD及(rac)α-HBCD溶液对发芽后的玉米幼苗进行暴露,开展α-HBCD对映体对植物生理和基因损伤作用研究.结果表明,不同α-HBCD对映体暴露后玉米根部形态发育异常,(+)α-HBCD处理的玉米根须明显稀疏;植物根部组织、地上部的生物量和长度的相对抑制率与暴露浓度线性相关,其中,(+)α-HBCD对玉米生长的抑制最强;玉米地上部叶绿素含量随α-HBCD暴露浓度的增加而显著降低,且降低量顺序为(+)α-HBCD(rac)α-HBCD(-)α-HBCD;低浓度的(+)α-HBCD显著诱导了玉米根部组织和地上部超氧化物歧化酶(SOD)和过氧化氢酶(CAT)的活性,高浓度时则表现为显著的抑制作用,其中,SOD对α-HBCD胁迫反应更为敏感;组蛋白H2AX的磷酸化(γ-H2AX)水平呈现出不同的变化趋势,其中,(+)α-HBCD诱导γ-H2AX焦点数量增加最为显著.综上,α-HBCD对映体对玉米生理和基因水平均产生了选择性损伤作用,(+)α-HBCD的损伤作用强于(-)和(rac)α-HBCD.本研究可为综合评价手性HBCD的环境行为和生态风险提供重要信息.     

Enantioselective induction of oxidative stress by acetofenate in rat PC12 cells

In a non-chiral environment,the enantiomers of a racemate possessed the identical physico-chemical properties,but in the biological systems they possessed different activities.Considering that the involvement of oxidative damage has been implicated in the toxicities of various pesticides,this study investigated the possibility of enantioselective oxidative stress and cytotoxicity induction by acetofenate (AF) which contains an asymmetrical center on PC12 cells.The results of the cytotoxicity assay indicated that S-(+)-AF presented more toxic effects than R-(-)-AF and (±)-AF.It also demonstrated that S-(+)-AF possessed the strongest effects in induction of reactive oxygen species (ROS) production,decrease in superoxide dismutase (SOD) and catalase (CAT) activities,and increase in malondialdehyde (MDA) level.These results suggested that AF and its enantiomers could induce enantioselective cytotoxicity in PC12 cells mediated by oxidative stress.Therefore,the assessment in environmental safety and new chiral pesticide development should consider enantioselectivity.     

The profiles of chiral pesticides in peri-urban areas near Yangtze River: Enantioselective distribution characteristics and correlations with surface sediments

Chiral pesticides account for 30% of pesticides. Pesticides are inevitably leached into the groundwater by runoff. At the watershed level, the distribution characteristics of enantiomers in sediments collected from the river network of an agricultural area near the middle and lower reaches of the Yangtze River were tested, and their potential correlations with the physicochemical properties and microbial communities of the sediments were analyzed. The sediment pollution was serious at sites 8 and 9, with their pollution source possibly being agricultural or industrial sewage. Moreover, there were higher cumulative contents of pesticide residues at sites 4, 8, and 9. Specifically, Cycloxaprid was the most detected chiral pesticide in the study area, followed by Dinotefuran and Diclofop-methyl. Additionally, Ethiprole and Difenoconazole had strong enantioselectivity in the study area. Interestingly, the enantiomers of some chiral pesticides, such as Tebuconazole, had completely different distributions at different sites. Pearson correlation analysis showed that sediment catalase and microbial biomass carbon were important factors for enantioselectivity of chiral pesticides. The effect of sediment physicochemical properties on enantioselective distribution was achieved by influencing the microorganisms in the sediment. Furthermore, the enantioselective distribution of Tebuconazole was closely related to the genus Arenimonas. Overall, the enantioselective distribution of most of the chiral pesticides was positively correlated with the prokaryotic microbial community. This study provides empirical support for agricultural non-point source pollution caused by chiral pesticides, and also lays a research foundation for exploring the factors that affect the fate of chiral pesticides in the environment.     

Enantioselective separation and zebrafish embryo toxicity of insecticide beta-cypermethrin

Enantioselectivity of chiral pollutants is receiving growing concern due to the difference in toxicology and environment fate between enantiomers.In this study,enantiomers of insecticide beta-cypermethrin (beta-CP) were separated on selected chiral column by HPLC,and the toxicity of enantiomers was evaluated using the zebrafish embryo-larval assays.The enantiomers of beta-CP were baseline separated on Chiralcel OD and Chiralpak AD columns and detected by circular dichroism (CD) at 236 nm.Better separation could be achieved at lower temperature (e.g.,20°C) and with lower levels of polar modifiers.Pure enantiomers were obtained on Chiralcel OD.The CD spectra of enantiomers were recorded.By comparing the elution order with a previous similar study,the absolute configuration of beta-CP enantiomers was determined.The individual enantiomers were used in zebrafish embryo test,and the results showed that beta-CP enantioselectively induced yolk sac edema,pericardial edema and crooked body.The 1R-cis-αS and 1R-trans-αS enantiomers showed strong developmental toxicities at concentration of 0.1 mg/L,while the 1S-cis-αR and 1S-trans-αR induced no malformations at higher concentration (e.g.,0.3 mg/L).The results suggest that the enantioselective toxicological effects of beta-CP should be considered when evaluating its ecotoxicological effects.     

基于非靶向物种保护的农药水环境基准及排放限值研究

我国农药行业的水污染排放管理长期以来缺乏对特征污染物的控制要求,特征污染物产生、处理和排放的数据基础也非常薄弱.鉴于农药活性成分对作用对象极其敏感但又具有高选择性的特点,可以立足于对敏感作用对象以外的水生生物加以充分保护的思路,建立基于非靶向物种保护的农药水环境急性基准,作为我国现阶段农药排放限值的推导基础.基于对几十种农药活性成分毒性数据的分析,将物种毒性数据敏感度变化最显著的位序点（累积概率在5%~30%之间）作为“靶向物种”与“非靶向物种”累积概率的分割点,提出保护非靶向物种目标的水质基准计算方法,并以毒死蜱为例,应用物种敏感度分布曲线法对特征污染物毒死蜱水质基准值进行示例推导.筛选出无脊椎动物、脊椎动物和植物等9门39科59种共109个急性毒性数据,经计算得出,毒死蜱对我国水生生物的HC_t（靶向物种的危害浓度）为4.35 μg/L,基于HC_t得到的毒死蜱排放限值为20 μg/L,与美国农药工业水污染物排放指南与排放标准中毒死蜱对现源的日最大排放限值（经换算为8 μg/L）较为接近.研究显示,基于非靶向物种保护的农药水环境基准方法推导的排放限值与发达国家排放控制要求接近,通过有效的污染控制技术可以实现,具有可达性.      

氰戊菊酯和锐劲特对原生动物群落的联合毒性试验研究

氰戊菊酯和锐劲特两种农药被广泛用于茶树、果树、水稻、蔬菜等的病虫害防治,它们同时出现在同一环境中的机会非常多,但有关两种农药对生态系统的复合毒性效应却未见有研究报道.与单种生物毒性试验相比,群落级生物毒性试验对毒物胁迫的反映更具环境真实性.以PFU在天然淡水中采集到的原生动物群落为靶生物,研究了氰戊菊酯和锐劲特2种农药对淡水原生动物群落的毒性效应,对于水生生态环境的保护有特殊的意义.研究结果表明,2种农药单独存在时对原生动物群落的48h半数致死浓度分别为15 93mg·L-1和35 83mg·L-1;2种物质以等毒性比(单一LC50的比值)混和,进行联合毒性试验研究,用Marking相加指数法进行评价,其AI值为0 9,表现为协同作用.氰戊菊酯和锐劲特进入水环境后,将使水环境中原生动物群落的结构和组成发生变化,原生动物种类数减少,群落结构变得简单.在所有种类中,纤毛虫受损最大,水生生态系统的物质循环和能量流动将会受到一定程度的影响.     

Mutagenic and cytotoxic potential of Endosulfan and Lambda-cyhalothrin - In vitro study describing individual and combined effects of pesticides

Excessive use of pesticides poses increased risks to non target species including humans. In the developing countries, lack of proper awareness about the toxic potential of pesticides makes the farmer more vulnerable to pesticide linked toxicities, which could lead to diverse pathological conditions. The toxic potential of a pesticide could be determined by their ability to induce genetic mutations and cytotoxicity. Hence, determination of genetic mutation and cytotoxicity of each pesticide is unavoidable to legislate health and safety appraisal about pesticides. The objective of current investigation was to determine the genotoxic and cytotoxic potential of Endosulfan（EN） and Lambda-cyhalothrin（LC）; individually and in combination. 3-（4,5-Dimethylthiazol-2-yl）-2,5-Diphenyltetrazolium Bromide（MTT） assay was utilized to determine cytotoxicity, while two mutant histidine dependent Salmonella strains（TA98, TA100） were used to determine the mutagenicity of EN and LC.Moreover, mutagenicity assay was conducted with and without S9 to evaluate the effects of metabolic activation on mutagenicity. Even though a dose dependent increase in the number of revertant colonies was detected with EN against both bacterial strains, a highly significant（p 〈 0.05） increase in the mutagenicity was detected in TA98 with S9. In comparison, data obtained from LC revealed less mutagenic potential than EN. Surprisingly,the non-mutagenic individual-concentrations of EN and LC showed dose dependent mutagenicity when combined. Combination of EN and LC synergistically induced mutagenicity both in TA98 and TA100. MTT assay spotlighted comparable dose dependent cytotoxicity effects of both pesticides. Interestingly, the combination of EN and LC produced increased reversion and cytotoxicity at lower doses as compared to each pesticide, concluding that pesticide exposure even at sub-lethal doses can produce cytotoxicity and genetic mutations, which could lead to carcinogenicity.     

Low concentrations of atrazine, glyphosate, 2,4-dichlorophenoxyacetic acid, and triadimefon exposures have diverse effects on Xenopus laevis organ morphogenesis

Many chemicals are released into the environment, and chemical contamination has been suggested as a contributing factor to amphibian declines. To add to a growing body of knowledge about the impact of individual chemicals on non-target organisms, we examined the specificity of deformities induced by exposure to four pesticides (atrazine, 2,4-dichloropheoxyacetic acid (2,4-D), triadimefon, and glyphosate) in the model amphibian species, Xenopus laevis. We focused on the period of organ morphogenesis, as it is frequently found to be particularly sensitive to chemical exposure yet also commonly overlooked.We found similar levels of intestine malformations and edemas, as well as disruption of skeletal muscle, in atrazine and triadimefon exposed tadpoles. The e ects of 2,4-D were only apparent at the highest concentrations we examined; glyphosate did not induce dramatic malformations at the concentrations tested. While researchers have shown that it is important to understand how chemical mixtures a ect non-target organisms, our results suggest that it is first crucial to determine how these chemicals act independently in order to be able to identify consequences of individual pesticide exposure.     

The convoluted evolution of snail chirality

The direction that a snail (Mollusca: Gastropoda) coils, whether dextral (right-handed) or sinistral (left-handed), originates in early development but is most easily observed in the shell form of the adult. Here, we review recent progress in understanding snail chirality from genetic, developmental and ecological perspectives. In the few species that have been characterized, chirality is determined by a single genetic locus with delayed inheritance, which means that the genotype is expressed in the mother's offspring. Although research lags behind the studies of asymmetry in the mouse and nematode, attempts to isolate the loci involved in snail chirality have begun, with the final aim of understanding how the axis of left-right asymmetry is established. In nature, most snail taxa (>90%) are dextral, but sinistrality is known from mutant individuals, populations within dextral species, entirely sinistral species, genera and even families. Ordinarily, it is expected that strong frequency-dependent selection should act against the establishment of new chiral types because the chiral minority have difficulty finding a suitable mating partner (their genitalia are on the 'wrong' side). Mixed populations should therefore not persist. Intriguingly, however, a very few land snail species, notably the subgenus Amphidromus sensu stricto, not only appear to mate randomly between different chiral types, but also have a stable, within-population chiral dimorphism, which suggests the involvement of a balancing factor. At the other end of the spectrum, in many species, different chiral types are unable to mate and so could be reproductively isolated from one another. However, while empirical data, models and simulations have indicated that chiral reversal must sometimes occur, it is rarely likely to lead to so-called 'single-gene' speciation. Nevertheless, chiral reversal could still be a contributing factor to speciation (or to divergence after speciation) when reproductive character displacement is involved. Understanding the establishment of chirality, the preponderance of dextral species and the rare instances of stable dimorphism is an important target for future research. Since the genetics of chirality have been studied in only a few pulmonate species, we also urge that more taxa, especially those from the sea, should be investigated.