氨基甲酸-2-氯吡啶-5-甲酯化合物的合成与抑菌活性

以芳香硝基化合物、2-氯-5-吡啶甲醇和一氧化碳为原料,在Pd-Fe/Ti O2催化下进行羰基化反应,合成了11个新型氨基甲酸-2-氯吡啶-5-甲酯化合物,其结构经1H NM R和M S表征。初步抑菌活性测定结果表明:在50 mg/L下,大多数目标化合物对4种供试病原菌具有一定的抑制活性,其中化合物3f(4-甲氧基苯基氨基甲酸-2-氯吡啶-5-甲酯、3h(2,4-二氯苯基氨基甲酸-2-氯吡啶-5-甲酯)和3j(3,4-二氯苯基氨基甲酸-2-氯吡啶-5-甲酯)对小麦赤霉病菌Gibberella zeae的抑制率达77.3%以上,3f对苹果轮纹病菌Physalospora piricola的抑制率达82.5%,与对照药多菌灵接近;所有化合物在50 mg/L下对番茄灰霉病菌Botrytis cinerea的抑制活性均优于对照药多菌灵。     

土壤环境因子对氯胺嘧草醚除草活性的影响

采用常规室内生物测定法,研究了土壤环境因子对氯胺嘧草醚[开发代号ZJ1835,化学名称为N-(2-氯-6-(4,6-二甲氧基嘧啶-2-氧基)苄基)苯胺]除草活性的影响。结果表明:土壤质地、p H值、有机质含量、土壤湿度和温度对其除草活性均能产生一定影响。氯胺嘧草醚在砂土和黏土中的活性高于壤土,其除草活性随土壤有机质含量、p H值和土壤湿度的升高而升高,而温度偏高或偏低均不利于其药效发挥,在15~25℃环境条件下除草活性最佳。     

6-甲基-4-羟基-2-吡喃酮及其3-羧酸衍生物的简便合成方法

6-甲基-4-羟基-2-吡喃酮1和它的3-羧基衍生物2是合成化学杂交剂(chemicalhybridiz-ingagent)fenridazon-k的关键中间体,也是一般有机合成的中间体。OOHRO　1　R=H2　R=COOHKang等[1]报道了一种大量制取2的方法:在三乙胺存在下,丙二酸亚异丙酯3与双乙烯酮反应得到化合物4,4在对甲苯磺酸的催化下,在甲苯中回流,脱丙酮、环合生成2:OOOO　　　3CH2OOEt3N,CH2Cl2OOOOOHO　　　　4CH3SO3HPhMe,△OOHCOOHO　　2Suzuki[2]等报道,2在155℃受热则脱羧生成1。OOHCOOHO　　2　155℃　-CO2OOHO　　1作者等发现:4是不稳定的化合…     

含2-氯-5-亚甲基吡啶基团的硫脲化合物的合成及生物活性

合成了 10个结构新颖的 2 -氯 - 5 -亚甲基吡啶的硫脲化合物 ,用 IR、1H NMR及元素分析对其结构进行了确证。植物生长调节活性的初步测定结果表明 :在 5 mg/ L时对水稻幼苗根的促生长率都大于 90 %。     

沙柳稳定碳同位素值的特点及其水分利用效率

通过对沙柳5个种源苗木叶片不同月份稳定碳同位素组成(1δ3C)的测定,研究不同种源沙柳δ13C值的特点,试图找出影响δ13C值季节变化的关键环境因子。结果表明:沙柳碳同位素值在-26.753‰~-29.915‰之间变化,其中,乌审旗和榆林种源1δ3C值较高,表明在该试验条件下具有较高的水分利用效率;叶片与枝条相比,δ13C值在6月和8月差异明显,达到0.930‰~2.469‰;而枝条的碳同位素值差异较小,为0.032‰~0.838‰;沙柳δ13C值在不同月份间有显著性差异,6月δ13C值明显高于8月;在将各环境因子分离开的情况下,主要研究了大气相对湿度对植物的1δ3C值季节变化的影响,结果显示,δ13C值随大气相对湿度的降低而偏重。     

2-氰基-3-取代胺基(或甲硫基)-3-(2-氯-5-吡啶甲胺基)-丙烯酸酯类化合物的合成及生物活性

作者曾模拟新烟碱类杀虫剂的化学结构,合成了一系列含2-氯-5-吡啶甲基的双氰基取代烯酮缩胺类化合物,并对其进行了生物活性测定,发现部分化合物显示了较好的杀虫和除草活性[1],特别是除草活性引起我们的兴趣。为进一步研究此结构类型的化合物的合成及生物活性,我们以酯基替代前文所述化合物中的一个氰基,并保留新烟碱杀虫剂nitenpyram类似物的骨架[2]。由于这种结构与作为光合作用光系统II(PSII)电子传递抑制剂的氰基丙烯酸酯类化合物很相似[3],该类化合物可能会有更好的除草效果。我们依此设计,合成了2-氰基-3-(2-氯-5-吡啶甲胺基)-3-甲…     

丙溴磷乳油中的2-氯-4-溴苯酚分析的新方法

研究了用高效液相法定量分析丙溴磷50％乳油中的2-氯-4-溴苯酚新方法.色谱条件如下：250mm×4.6mm （V/V）,5μm ODS不锈钢柱;流动相：甲醇∶水∶冰乙酸=85∶15∶0.3（V/V）;流速：1.0mL/min;可变紫外检测器：波长245nm.本方法在0.625μg～10μg进样范围内和峰面积（高）呈线性,相关系数值（R）为0.999 8.回收率在98％～102％之间,溴酚的平均回收率为100.1％.变异系数＜5％.     

吡啶衍生物研究(V):2-[(2-氯吡啶)-4-基]-5-芳胺基-1,3,4-噻二唑的合成及杀菌活性

合成了一系列 2 - [(2 -氯吡啶 ) - 4 -基 ]- 5-芳胺基 - 1,3,4 -噻二唑类化合物 ,其结构经元素分析、1H NMR、和 13 C NMR确认。初步生物活性测定表明 ,合成化合物对某些真菌生长表现出较好的抑制活性 ,如 I- 0 2在 50 0 μMg· m L-1剂量下对水稻纹枯病菌生长的抑制率达87.5%。     

准噶尔盆地南缘土壤水运移特征及其补给来源识别

在荒漠区,土壤水是一切陆生植物赖以生存的基础,识别荒漠区土壤水的补给来源,探索土壤水的运移机理,对于荒漠区生态修复非常必要。通过对荒漠区非饱和带剖面土壤水的含水率、易溶盐离子及稳定同位素(δD、δ~(18)O)的测定和分析,研究荒漠区土壤水的补给来源与运移机理。结果表明:荒漠区土壤含水率、易溶盐与土壤水氢氧同位素在垂向上呈现旋回变化,剖面中土壤Cl-含量与含水量成正相关;0~1.6 m为蒸发影响带,1.6~8.0 m为土壤水向下运移带,8.0 m以下为潜水影响带。从土壤水中氢氧同位素及Cl-含量信息来看,荒漠区土壤水来源于大气降水的补给。旋回中Cl-含量极低值与δD与δ~(18)O极贫值相对应,δD值贫化峰值为-124.10‰~-97.39‰,荒漠区土壤水来源于冬季大气降水或降雪的入渗补给。     

含苯丙氨酸和1H-茚-1-酮类氯虫苯甲酰胺类似物的合成及杀虫活性

为了开发新的杀虫化合物，以氯虫苯甲酰胺为先导，2-甲基-3-氨基苯甲酸为起始原料，经过卤化生成5-氯-3-甲基-2-氨基苯甲酸；再与3-溴-1-(3-氯吡啶-2-吡啶基)-1H-吡唑-5-甲酸进行缩合反应，生成6-氯-2-(3-溴-1-(3-氯吡啶-2-吡啶基)-1H-吡唑-5-基)-8-甲基-4H-3,1-苯并噁嗪-4-酮；最后引入苯丙氨酸片段并经环化反应，分别合成了两个系列共计23 个新化合物( 4 和 5 )，其中化合物 4 为含苯丙氨酸的氯虫苯甲酰胺类似物，化合物 5 为由化合物4环化生成的含1H-茚-1-酮片段的氯虫苯甲酰胺类似物，所有化合物的结构均通过核磁共振氢谱(1H NMR)、碳谱(13C NMR)和高分辨质谱(HRMS)的表征及确证。初步室内杀虫活性测试结果表明，多数目标化合物对黏虫Mythinma separata具有较高的杀虫活性，其中14个化合物在100 mg/L下对黏虫Mythinma separata的致死率为100%，化合物 5k ( 1H-茚-1-酮片段中取代基为羟基 ) 在4和0.8 mg/L下的致死率分别为90%和70%，其LC₅₀值为0.55 mg/L。分子对接结果表明，化合物 5k 与氯虫苯甲酰胺一样，也是作用于鱼尼汀受体(RyR)，但与靶标结合的氨基酸残基不同，这种差异可能对黏虫的抗药性治理研究有益。     

西藏雨季主要水体氢、氧同位素特征

通过对2014年雨季西藏境内63处水体中δD和δ~(18)O值的测定,分析其中氢、氧稳定同位素组成特征。结果表明:水体δD和δ~(18)O的取值范围分别为-152.06‰~-19.05‰和-16.96‰~4.66‰,δD较δ~(18)O的标准差大,平均值分别为-101.38‰和-9.67‰;3种水体的δD和δ~(18)O值关系为湖泊δD相对河流δD富集,河流δD相对沼泽δD富集,湖泊δ~(18)O相对河流δ~(18)O和沼泽δ~(18)O富集,河流δ~(18)O和沼泽δ~(18)O无差异;蒸发趋势方程分别为δD湖泊=6.14δ~(18)O-45.48(n=22,R2=0.855),δD河流=7.83δ~(18)O-26.22(n=32,R2=0.858),δD沼泽=5.93δ~(18)O-52(n=9,R2=0.723),河流相比湖泊和沼泽水体的δD与δ~(18)O更易受大气降水的影响;氘过量参数特征为湖泊-79‰~-17‰,河流-40‰~-5‰,湿地沼泽-34‰~-7‰,表现出蒸发强烈的水体特征;沼泽水体δ~(18)O与纬度的一元线性回归方程为y=1.67x-63.23。     

Distribution of isotopes and chemicals in precipitation in Shule River Basin,northwestern China:an implication for water cycle and groundwater recharge

The distribution of stable isotopes and ions in precipitation in the Shule River Basin,northwestern China,were investigated to understand the regional water cycle and precipitation input to groundwater recharge.The study found that the mean annual concentrations of Ca2+,Na+,SO42–,Cl–,Mg2+,NO3–,and K+ in the basin were lower than those in other arid areas of northwestern China.The average concentrations of ions in the lower reaches of the Shule River were higher than those in the upper reaches.The results showed that the main ionic concentrations decreased with the increase of precipitation amount,indicating that heavy precipitation cannot only wash crustal aerosols out of the atmosphere,but also create a dilution effect.Cl– and Na+ in precipitation had a strong and positive correlation,suggesting a common origin for the two ions.However,the excess of Na+,combined with non-marine SO42– and NO3–,indicated that some ions were contributed by terrestrial origins.In the extremely arid regions of northwestern China,the evaporation process obviously changes the original relationship between δ2H and δ18O in precipitation,and leads to dexcess values 8‰.δ18O and temperature were significantly correlated,suggested that temperature strongly affected the characteristics of isotopes in the study area.The δ18O value indicates a dominant effect of westerly air masses and southwest monsoon in warm months,and the integrated influence of westerly and Siberian-Mongolian polar air masses in cold months.The d-excess values were generally lower in warm months than those in cold months,indicating that post-condensation processes played a significant role in the water cycle.The results provide reliable precipitation input information that can be used in future groundwater recharge calculations in the study area.     

Raf-1 is dually down regulated by p,p′-DDE via reduced thyroid hormone and activated ERK

Raf-1 is the best characterized member of the mammalian raf family. The raf-1 kinase has many important physiological functions but its regulation is complex. 1,1-Dichloro-2,2 bis(p-chlorophenyl) ethylene (p,p′-DDE), a major and important metabolite of organochlorine pesticide DDT, is a widespread environmental pollutant. Previous studies have reported that p,p′-DDE influences the MAPK pathway, but little details are known regarding how the raf-1 activity is influenced and regulated by p,p′-DDE in those events. And here, we used 20 male rats that received different doses of p,p′-DDE (0, 20, 60, 100 mg/kg b.wt) every other day by intraperitoneal injection for 10 days. Results showed that the raf-1 mRNA and protein expressions showed significant down-regulation. The thyroxine (T4) level and the protein kinase C alpha (PKCα) mRNA expression declined, but the raf kinase inhibitory protein (RKIP) up regulated. In addition, the p,p′-DDE-induced oxidative stress resulted in declines of glutathione peroxidase (GSH-PX) and superoxide dismutase (SOD) activities. The elevations of ERK mRNA level and phosphorylated ERK protein expression were also observed. Taken together, these results suggest that the raf-1 is dually down regulated by p,p′-DDE via two pathways. One pathway is that the p,p′-DDE exposure elevates RKIP level by decreasing T4 and PKCα level, and the increased RKIP eventually down regulates the raf-1. The other is that the p,p′-DDE exposure activates the ERK by oxidative stress, and the activated ERK down regulates the raf-1 through the negative feedback phosphorylation.     

The concentrations of aldrin and dieldrin and their photoisomers in the atmosphere

Air samples taken in 1973 at a point remote from areas of organochlorine pesticide usage, Bantry Bay in S.W. Ireland, were analysed for aldrin and dieldrin in the vapour state and in association with particupate matter. In addition, some of the samples were analysed for the photoisomers of aldrin and dieldrin, and for pp'-DDT, 1,1-dichloro-2,2-di-(4-chlorophenyl) ethylene (pp'-DDE) and pp'-IDE. Detection and quantitation of all compounds were by gas-liquid chromatography with electron capture detection (g.l.c./e.c.). Confirmatory evidence for the presence of dieldrin and pp'-DDE was obtained with some samplesusing gas-liquid chromatography with mass fragmento-graphic detection (g.l.c./m.f.). Dieldrin was detected in all seventeen samples of air taken, but the mean concentration was 0.36 ng/kg and the range of concentrations was 0.06–1.60 ng/kg. Aldrin was not detected in the samples examined, neither were the two photoisomers. Only pp'-DDE of the pp'-DDT group of compounds was detected in the nine samples examined, and the apparent mean concentration was 0.14 ng/kg. None of the compounds was detected in particulate matter.     

乌鲁木齐大气降水稳定同位素与水汽来源关系研究

利用GNIP（Global of Isotope in Precipitation）乌鲁木齐站点1986-2003年大气降水稳定同位素资料和美国国家环境保护委员会/国家大气研究中心（NCEP/NCAR）再分析资料,通过研究乌鲁木齐地区17年（1986-2003）大气降水的氢、氧稳定同位素组成,提出了局地大气降水线方程为...     

Mechanisms of DDT resistance in larvae of the mosquito Aedes aegypti L

Larvae of eight strains of Aedes aegypti were exposed to DDT and compared for resistance, DDT uptake, in-vivo breakdown of DDT and residual unmetabolised DDT. Resistance varied widely between strains, three being fully susceptible, two almost immune and three of intermediate resistance. Breakdown of DDT by dehydrochlorination to 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (pp'-DDE) occurred in all strains and was greater in the five resistant types, but there was no significant correlation between the extent of breakdown in the resistant strains and the level of resistance. Moreover the overall difference between susceptible and resistant strains disappeared when they were compared at a low, almost sublethal, concentration of DDT. Larvae of resistant strains carried a greater absolute quantity of unmetabolised DDT in the body and were able to tolerate levels of DDT that were lethal to susceptible larvae. However the two most resistant strains (T8 and B51) contained significantly less DDT plus pp'-DDE than strains of intermediate resistance (T30 and BSJ) from which they had been derived. Addition of the synergist chlorfenethol to DDT increased its knockdown effect on all resistant strains, suggesting that dehydrochlorination was a factor in resistance. Three strains, two DDT-resistant and one DDT-susceptible, were tested with 1,1-bis(4-ethoxyphenyl)-2,2-dimethylpropane (I), an insecticide that cannot be dehydrochlorinated. All the strains were relatively tolerant to it although the DDT-susceptible strains were less tolerant. Addition of the synergist sesamex decreased the level of tolerance to I in all strains which suggested that microsomal oxidation made some contribution to it. It is concluded that three factors contribute to larval DDT resistance in A. aegypti; (a) increased metabolism to pp'-DDE; (b) increased tolerance to unmetabolised internal DDT; and (c) reduced content of DDT+pp'-DDE (only in the most resistant strains and due either to reduced absorption or increased excretion). These factors are discussed in relation to known larval resistance genes R^DDT1 and y.     

Comparative excretion of DDT analogues into milk of indian buffalo,Bubalus bubalis L. following oral administration

Four groups of Indian buffaloes were fed daily with 25 mg of p,p′-DDT p,p′-TDE p,p′-DDE or o,p′-DDT for 100 days. Milk was analysed for organochlorine residues during this period and also for 100 days after pesticide administration had been discontinued. For the period showing ‘plateau level’ residues, 17.2% of p,p′-DDE, 17% of p,p′-TDE, 14% of p,p′-DDT as p,p′-DDT (3.5%); p,p′-TDE (10.5%); 3.2% of p,p′-DDT as o,p′-DDT (1.3%) and o,p'-TDE (1.9%) of their administered amounts were excreted in the milk. Since these compounds were excreted at different rates, the residue levels in the milk expected from a given feed would depend on their concentration and proportional distribution in the feed. The maximum tolerable content of DDT analogues in feed was derived to be 0.1 mg kg^?1 (dry weight basis) by using the maximum accumulation coefficient and incorporation of the necessary safety margin. It is concluded that Indian buffaloes fed with rations contaminated with a total of DDT analogues below this limit will yield milk of acceptable quality. Following the termination of feeding with contaminated rations, the elimination of p,p′-DDE in the milk took the longest time and that of o,p′-DDT the shortest. These results suggest that the time required for the initial high residue concentration to decline to less than the legal limit would be determined by the relative amounts of DDE, TDE and DDT in the milk, after elimination of the potent source of contamination.     

Residues of DDT in cottonseed after spraying with DDT and torbidan

DDT at 1.12 and 2.24 kg/ha a.i. and Torbidan at 5 and 10 litre formulation/ha (1 and 2 kg DDT/ha) were sprayed five times on cotton over a period of 15 weeks. Seeds from the first pick of the crop were found to contain as residues pp′-DDT and pp′-DDE [1,1-dichloro-2,2-di- (4-chlorophenyl)ethylene]. The highest residue level (0.783 parts/10⁶) was found in seeds from Torbidan 10 litre/ha treatment.     

中亚哈萨克斯坦西部过去～30000年以来有机碳同位素变化及其意义

选取位于中亚干旱区哈萨克斯坦中西部的VA剖面作为研究对象,在AMS14C测年基础上,分析了该剖面记录的过去～30000年以来的有机碳同位素组成变化。结果表明:该剖面记录的过去～30000年以来有机质碳同位素值(δ13Corg)变化于-26.19‰--22.12‰之间,均值为-23.77‰,植被主要为C3植物,C4植物仅仅在末次冰盛期出现且其相对丰度极低。因此VA剖面土壤有机碳同位素组成变化主要反映的是C3植物对气候环境因子的响应,进一步对影响该地区植物碳同位素因素的分析发现,降水是控制该地区C3植物碳同位素变化的主要因素,即:降水增多导致C3植物碳同位素值偏负,可以用来指示研究区古降水变化趋势,CO2浓度以及温度仅仅在末次冰盛期对C3和C4植物相对丰度有一定的影响。     

保水剂与氮肥混施对土壤持水特性的影响

测定聚丙烯酰胺(PAM)、凹凸棒/聚丙烯酸(WT)和聚丙烯酸钠(HM)3种保水剂在浓度分别为2‰、5‰8、‰的NaCl、MgCl2、CaCl2、FeCl3、尿素、硝酸钾、氯化铵等7种溶液中的吸水倍率;用离心机法测定保水剂与氮肥混施条件下土壤的持水特性。结果表明:与去离子水比较,保水剂在盐溶液中的吸水倍率显著下降,且随着溶液浓度升高,保水剂的吸水倍率明显下降,对于同一盐溶液浓度,离子类型对保水剂吸水倍率的影响表现为:Na+Mg2+Ca2+Fe3+,WT保水剂表现出较强的抗离子特性;保水剂在不同氮肥溶液中的吸水倍率有较大差异,氮肥类型对保水剂吸水倍率的影响表现为:尿素硝酸钾氯化铵;保水剂与氮肥混合施入土壤能提高土壤的持水能力,但施入氮肥降低了保水剂的性能;推荐保水剂与氮肥混合使用时,施氮量不超过0.50 gN/kg干土,保水剂用量不超过6‰。