咪鲜胺及其代谢产物2,4,6-三氯苯酚在蘑菇及土壤中的残留动态

采用液相色谱-质谱联用仪和气相色谱法分别测定了咪鲜胺及其代谢产物2,4,6-三氯苯酚在蘑菇及土壤中的残留消解动态。结果表明,咪鲜胺在蘑菇及土壤中的消解动态均符合负指数方程,半衰期分别为3.5 d和20.3 d;2,4,6-三氯苯酚在蘑菇中的残留量随时间的变化呈现先增后减的趋势,而其在土壤中的残留量则仅表现出增长的趋势。     

Studies on BHC isomers and related compounds: VIII. Urinary metabolites produced from γ- and β-BHC in the mouse: Chlorophenol conjugates

Metabolites produced from γ-BHC and β-BHC in the mouse urine were purified and characterized. Most metabolites from the both isomers were not extractable by organic solvents, and were conjugates such as sulfates and glucuronides. After hydrolysis with an appropriate enzyme, the conjugates gave chlorophenols, among which 2,4,6-trichlorophenol existed most abundantly—about 25% in the total urine metabolites. 2,4-Dichlorophenol constituted also a significant portion.     

咪鲜胺及其代谢产物在橙汁中的残留检测方法研究

采用气相色谱电子捕获检测器(GC-ECD)研究了咪鲜胺及其代谢产物在橙汁中的残留检测方法,使用石油醚:丙酮(8∶2,V/V)提取,石油醚萃取净化,将咪鲜胺及其代谢产物在高温下与吡啶盐酸盐反应,待全部转化成其代谢产物2,4,6-三氯苯酚后进行测定。其在橙汁中的最小检出量为10-11 g,最低检测浓度为0.01mg/kg,咪鲜胺在橙汁中的平均添加回收率为72.5~109.1%,变异系数在5.7~9.7%之间,符合农药残留分析的要求。研究结果表明,咪鲜胺在常温和冷冻条件下的消解半衰期分别为:56.3d和105.0d。表明咪鲜胺在冷冻条件下降解缓慢。本实验优化了咪鲜胺衍生化过程与净化方法,具有快速准确、毒性小、灵敏度高、可同时检测多个样品等特点。     

咪鲜胺及其代谢物在水稻中的残留检测方法及残留动态

采用气相色谱电子捕获检测(GC-ECD)研究了杀菌剂咪鲜胺及其代谢物在水稻中的总残留量检测方法。经简单净化后将咪鲜胺及其代谢物在高温下与吡啶盐酸盐反应,转化为2,4,6-三氯苯酚进行测定。咪鲜胺在各样品中的添加回收率为72.9％ ~103.4％,变异系数在1.46％ ~9.38％之间。残留动态研究表明,咪鲜胺在水稻苗中消解较快,半衰期仅为3.4 d;到水稻收获时,在用166.6 mg/L浸种处理后的稻米和稻秆中分别检出了0.025和0.056 mg/kg的残留量,其他样本中均未检出咪鲜胺的残留。     

Oxidative metabolism of tetrachlorocyclohexenes,pentachlorocyclohexenes, and hexachlorocyclohexenes with microsomes from rat liver and house fly abdomen

Microsomal mixed-function oxidase systems from rat liver and house fly abdomen effectively metabolized isomers of 3,4,5,6-tetrachlorocyclohexene, 1,3,4,5,6-pentachlorocyclohexene, and 1,2,3,4,5,6-hexachlorocyclohexene to tetrachlorocyclohexenol isomers, 2,4,5,-trichlorophenol, and 2,3,4,6-tetrachlorophenol, respectively. The $\text{(}\text{346}\text{5}\text{)-isomer}$ of pentachlorocyclohexene gave also an abundant amount of pentachlorocyclohexenol isomers. As the metabolites of ($\text{36}\text{45}$)-, ($\text{35}\text{46}$)-, and $\text{(}\text{34}\text{56}\text{)-hexachlorocyclohexene}$, some compounds such as 1,2,4-trichlorobenzene, 1,2,3,4-tetrachlorobenzene, and pentachlorobenzene were more abundantly formed, respectively, than 2,3,4,6-tetrachlorophenol. These oxidative metabolic reactions were shown to mainly proceed via “ene-like” hydroxylation accompanied by double bond migration. Inhibition by CO, piperonyl butoxide, and SKF 525-A suggested that the “ene-like” hydroxylating enzyme was cytochrome P-450 dependent. The formation of an isomer of pentachlorocyclohexenol from $\text{(}\text{36}\text{45}\text{)-hexachlorocyclohexene}$ was also observed, and this reaction was activated by SKF 525-A.     

地下水浅埋区盐碱地滴灌条件下土壤盐分运移研究

综述了国内外地下水浅埋条件下土壤盐分运移机理研究,滴灌条件下盐碱地土壤盐分运移机理研究,土壤盐分运移模型研究的相关研究成果,为滴灌技术在改造和利用地下水浅埋盐碱土地资源的应用提供了思路,为预报土壤盐碱化提供科学依据,并为地下水浅埋盐碱土滴灌条件下土壤盐分运移规律的进一步研究提出一些建议,认为地下水浅埋区盐碱地滴灌条件下土壤盐分运移规律的研究仍是今后土壤科学的研究重点.     

Synthesis and antifungal activity of the proposed structure of a volatile compound isolated from the edible mushroom Hypsizygus marmoreus

We synthesized the proposed structure of an antifungal compound detected in the culture broth of the edible mushroom Hypsizygus marmoreus. Using the Evans aldol and Abiko–Masamune aldol reactions as the key steps, we synthesized all of the stereoisomers of the compound with high stereoselectivity. The GC retention times and the fragmentation patterns in the mass spectra of the synthesized isomers did not match those of the natural product. Therefore, this result may imply that it is necessary to reisolate the natural product and reconsider its structure. All of the synthesized isomers were found to exhibit antifungal activity against the phytopathogenic fungus Alternaria brassicicola. Due to their simple structures, the obtained isomers could be lead compounds for new pesticides.     

喷灌条件下作物光合作用及生长的研究进展

就国内外有关喷灌条件下作物光合作用及生长的研究成果进行了分析和评述,讨论了喷灌条件下作物的生态、生理因子之间的相互关系以及对农田小气候变化的适应机制,指出了该领域研究中存在的问题和今后应加强的研究方向。     

Soil dissipation and biological activity of metolachlor and S-metolachlor in five soils

The resolved isomer of metolachlor, S-metolachlor, was registered in 1997. New formulations based primarily on the S-metolachlor isomer are more active on a gram for gram metolachlor basis than formulations based on a racemic mixture of metolachlor containing a 50:50 ratio of the R and S isomers. The labelled use rates of S-metolachlor-based products were reduced by 35% to give equivalent weed control to metolachlor. However, several companies have recently registered new metolachlor formulations with the same recommended use rates for weed control as S-metolachlor. This research was done to compare the soil behaviour and the biological activity of metolachlor and S-metolachlor in different soils under greenhouse and field conditions. Although K(d) ranged from 1.6 to 6.9 across the five soils, there were no differences in the binding of metolachlor and S-metolachlor to soil or in the rate of soil solution dissipation in a given soil. However, both greenhouse and field studies showed that S-metolachlor was 1.4-3-fold more active than metolachlor against Echinochloa crus-galli (L.) Beauv. in five different soils and that S-metolachlor was more active than metolachlor in three Colorado field locations. When the rates of metolachlor and S-metolachlor were adjusted for S isomer concentrations in the formulations, there were no differences between the formulations in field, greenhouse or bioassay studies. Thus herbicidal activity is due to the S isomers, with the R isomers being largely inactive.     

Chemistry,stereochemistry and biological properties of KWG 4168

KWG 4168 (8-tert-butyl-1,4-dioxaspiro[4,5]decan-2-ylmethyl(ethyl)(propyl)amine; proposed common name spiroxamine) is a new fungicide consisting of four biologically active isomers (two diastereomers, four enantiomers). The four isomers were separated by preparative HPLC on a chiral stationary phase. The diastereoisomers were synthesised from the corresponding chirally pure glycerol derivatives and were separated by preparative HPLC. COSY, HSQC and NOESY NMR spectroscopy were used to asign the configuration of the amino residue relative to the cyclohexyl ring. Studies of the activity against wheat powdery mildew, as well as the inhibition of sterol biosynthesis in fungi by the four stereoisomers, indicate the contribution of each isomer to the biological activity of spiroxamine.     

Mechanisms for the generation of reactive oxygen species in plant defence – a broad perspective

In response to attempted invasion by a pathogen, plants mount a broad range of defence responses, including the generation of reactive oxygen species (ROS). The most spectacular and one of the earliest observable aspects of this mechanism is the oxidative burst – a rapid and transient production of large amounts of ROS. This review is intended to provide a broad perspective on the multiplicity of mechanisms and signal transduction pathways leading to a single phenomenon of ROS generation in plant defence reaction to microbial infection. Thus, two major models describing the origin of ROS in the oxidative burst are presented, namely: the NADPH oxidase system analogous to that of mammalian phagocytotic cells, and the pH-dependent generation of hydrogen peroxide by exocellular peroxidases. Additionally, the involvement of other plasma membrane-bound proteins, utilizing NADH or NADPH, in ROS generation is also demonstrated. Furthermore, other exocellular enzymes, like germin/oxalate oxidases and amine oxidases producing ROS in response to pathogen infection are described. The potential participation of protoplastic ROS-generating systems residing in mitochondria, peroxisomes, and glyoxysomes constitutes the next part of this review. Finally, the potential elements of the signal transduction pathways leading to the activation of various mechanisms of ROS production are indicated.     

Persistence of gamma-BHC and beta-BHC in Indian rice soils under flooded conditions

The relative persistence of [¹⁴C]-gamma-BHC and [¹⁴C]-beta-BHC in Indian rice soils under flooded conditions was studied. In alluvial, laterite and pokkali (acid sulphate, saline) soils, rapid degradation of both isomers occurred; in sandy and kari (acid sulphate, saline) soils, both isomers persisted even after 41 days of flooding. The rapid degradation of BHC isomers in the former three soils was related to highly negative redox potentials within 20 days of flooding in contrast to oxidised conditions in sandy and kari soils even after 41 days. During the degradation in the soils, beta-BHC showed longer lag than gamma-BHC. Results suggest that the degradation of beta-BHC commences at a potential lower than that required for gamma-BHC degradation. Greater decomposition of gamma-BHC occurred in rice straw-amended soils than in unamended soils when the insecticide was incorporated to the soils in an aqueous solution. Addition of BHC isomers to the soils in ethanol resulted in comparable rates of rapid decomposition in both rice straw-amended and unamended soils, since ethanol was as effective as rice straw in lowering the redox potentials of the soils favouring BHC decomposition in unamended soil as well.     

Herbicidal action of clove oil on cucumber seedlings

The herbicidal action of clove oil on cucumber seedlings was characterized under light and dark conditions. Paraquat showed herbicidal activity only under the light condition, whereas the clove oil displayed herbicidal activity in both the light and the dark condition. Specifically, wilting and water content reduction progressed rapidly under both the light and the dark condition 1 h after the clove oil treatment, whereas the paraquat damage occurred only under the light condition 5 h after treatment. The malondialdehyde concentration increased more with the clove oil treatment than with the paraquat treatment under the light and dark conditions. The superoxide dismutase (SOD) activity was stimulated, but the catalase activity decreased in the clove oil treatment. In contrast, both the SOD and catalase activity decreased in the paraquat treatment. These results suggest that clove oil exerts herbicidal effects through a mechanism that is different from that of paraquat.     

森林生态保护与效益补偿法律机制研究

回顾了森林生态保护与效益补偿机制研究现状与存在问题 ,分析了传统的生态保护政策法律手段的作用和历史局限性 ,指出在市场经济条件下 ,法律机制是生态保护和效益补偿机制的主要保障。着重研究了森林生态补偿法律关系中的主体、客体、补偿强度、补偿方法 ;从立法、执法、监督以及产权改革等方面 ,系统提出了建立我国森林生态补偿法律机制的途径和措施     

Indol-3-ylacetic acid- and calmodulin-regulated Ca2+-ATPase: A target for the phytotoxic action of hexachlorocyclohexane

In rice seedlings, the organochlorine insecticide hexachlorocyclohexane (HCH) and its four major isomers—α,β, γ, and δ—have been shown to elicit their phytotoxic action by interacting with indol-3-ylacetic acid (IAA)-regulated growth and Ca²⁺-ATPase activity. When rice seedlings were grown in the presence of 0.34 mM HCH, seedling vigour was reduced to 33% of the control. A similar effect was observed when seedlings were grown in the presence of the γ and δ isomers, but not with the α and δ isomers of HCH. This reduced vigour could be restored by treating the seedlings with 100 nM IAA, suggesting that HCH and its isomers (γ and δ) limit either IAA synthesis or action or both. In a microsomal fraction from rice seedlings grown in the presence of either HCH or its isomers, the calmodulin-regulated Ca²⁺-ATPase activity was inhibited as follows: technical HCH = 46%, α isomer = 80%, β isomer = 72%, γ isomer = 65% and δ isomer = 62% of the control value, respectively. TLC analysis suggested that the various isomers of HCH are metabolised by the plant, except for the δ isotner, which accumulated. This isomer, along with the degraded products of other isomers, may be responsible for the phytotoxic action of HCH.     

不同水分状况对箭杆杨叶中输导组织及叶肉组织的影响

自然条件下水分状况对箭杆杨叶中输导组织及叶肉组织有一定的影响。水分状况好的叶中导管管腔直径大于水分状况差的，而管壁厚度却相反，水分状况差的导管管壁厚度大于水分状况好的。此点与试验条件下所得的结果略有差异，原因在于，试验条件下所用的材料为植物的幼茎或同化枝，而此项工作所用的材料为叶，在对干旱环境及水分状况变化的适应上，叶比茎或同化枝更为敏感。叶肉中栅栏组织在水分状况较差时发育程度比水分状况时高。无论     

Toxicology and metabolism of some synthetic pyrethroids in larvae of susceptible and resistant strains of the cattle tick boophilus microplus (Can.)

Larvae of the Malchi and DDT-R pyrethroid-resistant strains of ticks, compared with larvae of the Yeerongpilly (susceptible) strain, exhibited knock-down resistance equally to (1 RS)-cis- and (1 RS)-trans-permethrin but little resistance to either (1 RS)-cis- or (1 RS)-trans-cypermethrin. Kill resistance was higher in Malchi than in DDT-R ticks and more pronounced against the permethrin isomers. The cis-isomers were more potent overall than the trans-isomers. Cypermethrin isomers penetrated more slowly than permethrin isomers, especially into Malchi larvae. Metabolic detoxication, mainly esteratic, was fastest in Malchi larvae, trans-isomers consistently being attacked faster than cis-isomers. The greatei resistance of Malchi ticks is therefore probably due to a combination of these two differences. Dual mechanisms of the toxic action of pyrethroids are discussed.     

The pyrethrins and related compounds: X.—The methylbenzyl chrysanthemates

New or improved routes are used to prepare all the nineteen methylbenzyl chrysanthemates, including 2,4,6-trimethylbenzyl (+) and (?)-trans-chrysanthemates, 2,3,4,6-tetramethyl-and 2,3,4,5,6-pentamethyl-benzyl chrysanthemates, and the chrysanthemates of the new alcohols, 2,3,5-and 3,4,5-trimethylbenzyl alcohols.     

Disappearance of endosulfan residues from seawater and sediment under laboratory conditions

The dissipation rate of endosulfan isomers (α and β) in seawater and sediment was studied. The disappearance rate of both isomers from seawater and pure water was compared, and the same measurements were made in both sterile and unsterile marine sediment. Flasks of water and sediment, fortified with a dispersion of a commercial endosulfan 350 g litre⁻¹ EC, Protodan 35®, were incubated under laboratory light at room temperature for 82 days. A micro on‐line extraction method and GC‐ECD was used to determine the pesticide and its metabolites. The dissipation of endosulfan (in two phases of first‐order kinetics) occurred more rapidly in seawater than in pure water. At the end of the experiment, the concentration of α‐endosulfan in sterile sediment was four times greater than in unsterile sediment, while the dissipation rate of β‐endosulfan in unsterile sediment was approximately double that observed in sterile sediment. The dissipation of both forms in sediment occurred in a single stage. Endosulfan β‐isomer was more persistent than α‐isomer in both sterile and unsterile sediment. Dissipation of endosulfan sum of α‐ and β‐isomers in sediment at the end of the experiment ranged from 80% (sterile) to 95% (unsterile). Endosulfan sulfate was detected in water and sediment as the main metabolite. © 2000 Society of Chemical Industry     

Photolysis of pirimicarb in water under natural and simulated sunlight conditions

The photostability of pirimicarb, (2-dimethylamino-5,6-dimethylpyrimidin-4-yl dimethylcarbamate) in aqueous media, under natural and artificial sunlight irradiation conditions, is reported. The pH of the irradiated solutions remained constant during degradation time. The photodegradation mechanism seemed to be similar under both conditions, but the half-life was found to be about three times longer under natural than under artificial conditions. Four main photo-products ( 1 , 2 , 3 and 4 ) were isolated and identified by spectroscopic methods. It is proposed that a common photodegradation pathway exists for pirimicarb under both irradiation conditions. The results obtained from the photodegradation of pirimicarb and of its four main products isolated on solid phase permit the construction of a possible photodegradation pathway. Photoproduct 4 (2-methyl-formylamino-5,6-dimethyl-4-hydroxypyrimidine) is here described for the first time.