Acidic derivatives of the fungicide fenpiclonil: effect of adding a methyl group to the N-substituted chain on systemicity and fungicidal activity

A new acidic derivative of the fungicide fenpiclonil was synthesized containing a methyl group on the alpha-position of the carboxyl function of N-carboxymethyl-3-cyano-4-(2,3-dichlorophenyl)pyrrole. The phloem mobility of the resulting N-(1-carboxyethyl)-3-cyano-4-(2,3-dichlorophenyl)pyrrole was comparable with that of the former compound, but was higher at external pH 5.0. Unlike the derivatives previously synthesized, it was comparable with fenpiclonil in its fungicidal activity against the pathogenic fungus Eutypa lata.     

Measurement of xylem translocation of weak electrolytes with the pressure chamber technique

Xylem translocation and root uptake of weak electrolytes were investigated with the pressure chamber technique (PCT) using de-topped soybean plants. Two compounds were organic bases (fenpropimorph and imazalil) and four were organic acids (bentazone, primisulfuron-methyl, rimsulfuron and triasulfuron). The compounds covered a wide range of log KOW and pKa values. Concentrations in external solution and in xylem sap were measured by HPLC at pH values in external solution of 4.5, 6.5 and 8.5. For weak bases, translocation was higher at low pH and the transpiration stream concentration factors (TSCF) were in the range 0.31-0.95. At pH 8.5, the concentrations in leaking xylem sap were very low for fenpropimorph, and steady-state was probably not reached. For weak acids, TSCF values derived with external pH from 4.5 to 8.5 were in the range 0.55-1.50 for primisulfuron-methyl, 0.64-1.35 for rimsulfuron, 0.81-0.93 for triasulfuron and 0.69-0.92 for bentazone. The variation of TSCF of the weak electrolytes was much smaller in these PCT experiments than in recent experiments with intact plants. The likely reason is that de-topped soybean plants in the pressure chamber seemed to be unable to regulate their xylem sap pH, which was almost identical to the pH in external solution. Without pH differences, the ion-trap process, which is responsible for accumulation or exclusion of weak acids and bases in the xylem of living plants, does not take place. Model simulations carried out for intact and de-topped plants supported this hypothesis. By variation of the pH of the xylem sap, good agreement between measurements and simulations could be achieved.     

极端干旱区3种植物液流特征及其对环境因子的响应

运用热平衡法包裹式茎流计,对塔克拉玛干沙漠南缘地区优势植物种梭梭(Haloxylon ammodendron)、头状沙拐枣(Calligonum caput-medusae)和疏叶骆驼刺(Alhagi sparsifolia)（以下简称骆驼刺）生长季茎干液流速率变化规律进行持续观测。利用自动气象站对气象因子如太阳辐射(Rs)、气温(Ta)、相对湿度(RH)以及风速进行同步观测,并对气象因子与不同植物液流速率之间的相关关系进行分析。结果表明:① 梭梭液流速率日变化趋势为双峰或多峰型,表现出明显的“午休”现象,而头状沙拐枣呈单峰或多峰型,骆驼刺则表现为单峰型,两者均没有明显的“午休”现象;头状沙拐枣与骆驼刺液流启动时间比梭梭延后1 h左右,却提前1 h左右到达液流峰值,液流速率下降时间基本一致;② 整个生长季中,梭梭单枝液流量均保持较高水平,在7月达到最大值,而头状沙拐枣和骆驼刺则在8月时达到最大值;③ 3种植物在不同天气条件下液流速率大小依次为：晴天>沙尘暴>阴天>雨天;④ 3种植物液流速率与太阳辐射(Rs)、空气温度(Ta)和空气水汽压差(VPD)呈极显著的正相关(P<0.01),与空气相对湿度的关系则表现为极显著的负相关(P<0.01)。     

Effects of deficit irrigation on daily and seasonal variations of trunk sap flow and its growth in Calligonum arborescens

Water deficit in arid and semiarid regions affects whole-plant sap flow and leaf-level water relations. The objectives of this study were to clarify how sap flow of Calligonum arborescens responds to different drought stress conditions and to understand its acclimation mechanism to drought environments. A field experiment was conducted for C. arborescens during the growing season to evaluate the effects of deficit irrigation on the daily and seasonal variations of trunk sap flow in the shelterbelt along the Tarim Desert Highway, Xinjiang, China. Three different water regimes (2,380, 1,960 and 1,225 m3 /hm2 ) were applied at different stages of plant growth. From 1 May to 30 October 2007, a heat-balance stem flow gauge was used to monitor the sap flow dynamics of C. arborescens under different water regimes. Atmospheric evaporation demand and soil moisture conditions for differentially irrigated C. arborescens were also monitored. The result showed that sap flow exhibited a clear diurnal pattern regardless of treatments; the diurnal patterns of sap flow and vapour pressure deficit were very similar under different water regimes and growing seasons, while the slope of the linear regression of this correlation confirmed an increasing water regime. The sap flow decreased under reduced water regimes and there was nocturnal sap flow regardless of water regimes, which was mainly contributed to nocturnal transpiration and water recharge. The sap flow peaked before midnight and dropped afterwards with obviously higher values in summer than in other seasons. It is speculated that the water consumption of C. arborescens during the day can be supplemented through the sap flow at night, which increased with increasing irrigation amount. Net radiation was the most significant correlated factor that influenced sap flow velocity and transpiration under different water regimes (R2 >0.719). Compared with the commonly practiced water regime, the growth of C. arborescens was significantly slower in the stress deficit irrigation, but not significantly different from that in the moderate deficit irrigation. The moderate deficit irrigation would not affect the stability of the shelterbelt and was a more efficient use of water resources compared with the current watering amount.     

柴达木盆地沙棘茎流速率与环境因子的关系

采用热扩散flow-32包裹式茎流计,于2014年6—9月对柴达木盆地的沙棘茎流速率进行连续观测,并应用Vantage Pro 2小型气象站对林地的太阳辐射、大气温度、相对湿度主要气象因子进行同步采集,对不同天气条件下沙棘茎流速率的变化规律以及茎流速率与主要气象因子的相关关系进行研究。结果表明:典型晴天下沙棘茎流日变化呈双峰型,典型阴天下沙棘茎流呈单峰型,晴天的平均茎流速率是阴天的2.87倍;生长季各月的平均茎流速率为:8月7月9月6月;6—9月沙棘茎流速率与温度、太阳辐射呈极显著正相关(P0.01),与湿度呈极显著负相关(P0.01),各气象因子相关系数绝对值为:太阳辐射(0.811)大气温度(0.594)湿度(-0.571),太阳辐射是主导环境要素;用SPSS软件针对上述3种环境因子进行多元线性逐步回归,得回归模型Fs=19.268-0.221Ta-0.055RH+0.036Rs(R2=0.82),能够对柴达木盆地的沙棘蒸腾耗水量进行预测。     

The metabolism of cypermethrin in plants: The conjugation of the cyclopropyl moiety

The metabolism of the pyrethroid insecticide cypermethrin ([S,R,]-α-cyano-3-phenoxybenzyl-(1R,1S,cis,trans)-2,2-dimethyl-3-(2′,2′-dichlorovinyl)cyclopropane carboxylate), I, has been examined in lettuce plants grown and treated twice under outdoor conditions with ¹⁴C-cyclopropyllabeled material. The application rate at each treatment was equivalent to 0.3 kg/ha. At harvest, 21 days after the last application, the plants contained mainly unchanged cypermethrin (33% of the total radiolabel present) and polar materials (54%) which were shown to be conjugates of trans-2(2′,2′-dichlorovinyl)-3,3-dimethylcyclopropane carboxylic acid (II). One of these was identified as the β,d-glucopyranose ester. In separate experiments the uptake and metabolism of the acid (II) in cotton leaves were examined in the laboratory and the acid was shown to be readily converted into a mixture of the β,d-glucopyranose ester, an acidic derivative of this, and disaccharide derivatives including the glucosylarabinose ester and the glycosylxylose ester. Subsequently, cotton leaves were exposed to solutions of these individual conjugates, and interconversions between these metabolites were observed.     

不同程度干旱胁迫及复水对春玉米(丹玉39)茎流动态的影响

利用大型移动防雨棚开展了玉米干旱胁迫及复水试验,通过分析玉米植株茎流速率变化规律,揭示了不同程度干旱胁迫及复水对玉米植株茎流速率的影响及其对环境因子的响应规律。结果表明:1不同发育期干旱胁迫及对照试验的玉米植株茎流速率在晴天均呈单峰曲线,在阴天或多云天呈现不规则的上下波动状态;干旱胁迫导致玉米茎流速率显著下降并且峰值提前;复水后的茎流速率与对照间的差异缩小,但仍低于对照且峰值提前;2比较拔节—吐丝期茎流速率平均值为:对照重度干旱胁迫中度干旱胁迫,吐丝—乳熟期和乳熟—成熟期均为:对照中度干旱胁迫重度干旱胁迫。3茎流速率与净辐射、气温呈现显著正相关,与相对湿度呈现显著负相关;重度干旱胁迫后,土壤水分的亏缺影响了玉米植株茎流速率,减弱了相对湿度对其茎流速率的影响。     

额济纳绿洲中柽柳耗水规律的研究

本文利用热脉冲技术对黑河下游额济纳绿洲的柽柳灌丛液流进行了测定。结果表明:在正常生长下,柽柳在开始生长的初期(5-6上旬),单位面积液流通量为0.05-0.08L.cm-2.d-1;日平均耗水量为0.8-1.2L.d-1,在生长旺盛时期,液流通量为0.06-0.108L.cm-2.d-1;日平均耗水量为1.1-1.5L.d-1;在生长的后期(6月-9月),液流通量明显下降(9月下旬-10月),液流通量为0.04-0.06L.cm-2.d-1;在液流的日变化中,树液流速具有的多峰变化趋势,在中午有短暂液流明显减小的现象,晚上有明显液流上升,以补充树冠部分的水分储存;随着胸径的增大,茎流速率和茎流量也随之增大;在生长季节地径4-5cm的柽柳日平均耗水量1.25L,整个生长季节耗水量为150.8L。     

The metabolism of fenvalerate in plants: The conjugation of the acid moiety

The metabolism of the pyrethroid insecticide fenvalerate [(RS)-α-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutyrate] ( I ), and of its most insecticidal (αS,2S) isomer ( II ), has been examined in cabbage plants grown and treated under laboratory conditions with [¹⁴C]chlorophenyl- and [ring-¹⁴C]benzyllabelled preparations of the two compounds. Both insecticides disappeared from the treated leaves with similar half-lives of approximately 12–14 days; they underwent ester cleavage to a significant extent, together with some hydroxylation at the 2- or 4-position of the phenoxy ring, and hydrolysis of the nitrile group to amide and carboxyl groups. Most of the carboxylic acids and phenols thus produced occurred as glycoside conjugates. In separate experiments, the uptake and metabolism of 2-(4-chlorophenyl)-3-methylbutyric acid ( X ), the acidic half of the molecule, were examined in the laboratory, using abscised leaves of kidney bean, cabbage, cotton, cucumber and tomato plants. The acid X was found to be readily converted, mainly into glucose and 6-O-malonylglucose esters in kidney bean, cabbage and cucumber plants, into glucosylxylose, sophorose and gentiobiose esters in cotton, and into two types of triglucose esters with differing isomerism in tomato. One of the acetyl derivatives of the trisaccharide conjugates was identical with the synthetic deca-acetyl derivative of the [1 → 6]-triglucose ester.     

Advances in the potentiometric determination of pka and log kow of pesticides

The phenylpyrrole fungicide fenpiclonil inhibited the metabolism of glucose in mycelium of Fusarium sulphureum Schlecht at a concentration which only slightly inhibited mycelial growth (EC₁₅). At the same concentration, fenpiclonil also inhibited accumulation and, to a greater extent, phosphorylation of 2-deoxy[U-¹⁴C]glucose in starved mycelium loaded with unlabelled 2-deoxyglucose. Fenpiclonil did not affect cell-free phosphorylation of 2-deoxyglucose or the ATP content of mycelium. Therefore, the primary mode of action of the fungicide may be based on inhibition of transport-associated phosphorylation of glucose. This may cause a cascade of metabolic events which eventually lead to fungal growth inhibition and death. One major event affected by inhibition of transport-associated phosphorylation is the accumulation of polyols, such as glycerol and mannitol, in mycelium. This was not observed in an osmotically sensitive, fenpiclonil-resistant laboratory isolate of the fungus.     

Degradation of the herbicide flamprop-methyl in soil under anaerobic conditions

The degradation of the wild oat herbicide flamprop-methyl [MATAVEN, methyl (±)-N-benzoyl-N-(3-chloro-4-fluorophenyl)-2-aminopropionate] was studied in soils stored under anaerobic conditions. Comparative experiments were carried out in which soil was either covered with water or stored in an atmosphere of nitrogen. Under these anaerobic conditions, the major product was the carboxylic acid analogue (II) of flamprop-methyl, which was also a major degradation product formed in soil stored under aerobic conditions. However, the 2-, 3-, and 4-hydroxy-benzoyl analogues of II were also detected in soils stored under nitrogen or water and they were present in highest concentrations in the waterlogged soil. A further new product was also detected in waterlogged soil and it was shown to be N-benzoyl-N-(3-chloro-4-hydroxyphenyl)-2-aminopropionic acid. Although no hydroxylated derivatives of flamprop-methyl were detected in soils stored under aerobic conditions, it is possible that they were formed but underwent further degradation.     

Evaluation of a broad variety of coumarins,chromones, their furohomologues and thione analogues as phototoxins activated by UVA and visible light

The potential of a new kind of light-induced pesticide action was evaluated for a broad variety (32) of natural photosensitizers and their thione derivatives. The latter were synthesized to shift the absorption spectra towards the visible region and to increase the triplet and singlet oxygen quantum yields. Qualitative and quantitative evaluation of growth inhibition of Fusarium culmorum (F. G. Smith) Sacc. produced by these photosensitizers under UVA and visible light was performed on silica gel plates and in liquid medium. The results show that the phototoxicity per excited molecule of the thione derivatives using UVA light was similar to that of their parent natural compounds. On the other hand, only the thione derivatives were photoactive under visible light irradiation. These compounds show encouraging levels of phototoxicity against F. culmorum, both in liquid culture and on silica plates, and may have potential for use as photoactive pesticides.     

春小麦蒸腾测定中茎流计的标定及其应用

通过人工气候生长室盆栽试验,在对不同珍珠岩覆盖量下的土壤蒸发特征进行分析的基础上,采用由热平衡原理设计的茎流计对三个水分处理(高85％ ～ 75％、中65％～55％、低45％ ～ 35％)下的盆栽春小麦蒸腾特征进行研究并依据称重法结果加以标定,结果表明:(1)珍珠岩覆盖量为0.11 g/cm2时能够达到较好效果,并据此换算出测定时段春小麦实际蒸腾量占总蒸散量的比值为83.04％;(2)单株小麦茎流速率与蒸腾速率的回归分析得出相关系数r=0.92,方程斜率与截距值分别为0.4463和8.3391,以小时(h)为单位的回归分析结果与以天(d)为单位的类似;(3)以2012年10月31日为例,标定后单株小麦蒸腾速率分别为:高26.51 g/d、中17.13 g/d、低12.71g/d.采用茎流计法测定田间作物蒸腾时对测定结果加以标定是非常必要的.     

不同培养条件下甲霜灵在蓖麻幼苗韧皮部的输导性

甲霜灵是一种能通过植物叶片吸收后在韧皮部向下传导的杀菌剂,为了探明其在韧皮部的传导规律,以蓖麻幼苗为模式植物,通过改变试验过程培养液中甲霜灵含量、pH值以及培养的温度、时间及光照等因子,采用气相色谱-质谱联用 (GC-MS) 方法,检测了不同培养条件下蓖麻幼苗韧皮部渗出液中甲霜灵的含量。结果表明:光照对甲霜灵在蓖麻幼苗韧皮部中的输导性无显著影响;当培养液中甲霜灵质量浓度为400 mg/L时,其在蓖麻幼苗韧皮部中输导量最大;当培养液pH值为5.5时,甲霜灵在蓖麻幼苗韧皮部中输导量最大;当培养温度为28 ℃时培养效果最佳,温度过高或过低均会使甲霜灵在蓖麻幼苗韧皮部中的输导量减少;培养3 h以上,蓖麻幼苗韧皮部渗出液中甲霜灵的含量显著高于前2 h渗出液中甲霜灵的含量。该研究优化了蓖麻幼苗获得药剂最大吸收时的适宜培养条件,为检测其他未知化合物在植株韧皮部中的输导性提供了参考。     

3-苄基-5-(1-(2-氧代-1-氧杂螺[4,5]癸-3-烯-3-基)亚乙基)-2-氨基咪唑啉-4-酮类化合物的合成及杀菌活性

为寻找高活性的杀菌化合物,在前期合成5-(1-(4-甲基-2-氧代-1-氧杂螺[4,5]癸-3-烯-3-基) 亚乙基)-2-氨基咪唑啉-4-酮类化合物的基础上进行结构修饰,在咪唑啉-4-酮的3-位引入苄基,设计并合成了一系列未见文献报道的化合物,其结构经过核磁共振氢谱 (1H NMR)、碳谱 (13C NMR) 及高分辨质谱 (HR-ESI-MS) 确证。经高效液相色谱 (HPLC) 分析显示,Z-构型中间体化合物 6 在酸性条件下会发生氮质子化开环再环化,转化为E-构型化合物 7 。离体杀菌活性测定结果表明,3-位苄基的引入改善了该类化合物的杀菌活性,其中化合物 (E)-3-苄基-5-(1-(4-甲基-2-氧代-1-氧杂螺[4,5]癸-3-烯-3-基) 亚乙基)-2-(4-甲氧基苯基) 氨基-咪唑啉-4-酮 ( 9c ) 和 (E)-3-苄基-5-(1-(4-甲基-2-氧代-1-氧杂螺[4,5]癸-3-烯-3-基) 亚乙基)-2-(4-氟苯基) 氨基-咪唑啉-4-酮 ( 9h ) 对油菜菌核病菌的EC₅₀ 值分别为14.3和21.1 mg/L。活体杀菌活性测试结果显示,在400 mg/L下化合物 9c 对于黄瓜霜霉病和小麦白粉病的防治效果分别为 80%和85%。     

New 2-phenyl-4,5,6,7-tetrahydro-2H-indazole derivatives as paddy field herbicides

A series of 3-chloro-2-(4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-indazole derivatives containing various substituted isoxazolinylmethoxy groups at the 5-position of the benzene ring were synthesized and their herbicidal activities assessed under greenhouse and flooded paddy conditions. Among them, compounds having a phenyl or cyano substituent at the 3-position of the 5-methyl-isoxazolin-5-yl structure demonstrated good rice selectivity and potent herbicidal activity against annual weeds at 16-63 g AI ha(-1) under greenhouse conditions. Field trials indicated that these two compounds controlled a wide range of annual weeds rapidly with a good tolerance on transplanted rice seedlings by pre-emergence application. They showed a low mammalian and environmental toxicity in various toxicological tests.     

黄土源区施加磷肥对小麦光合性能、水分利用效率及茎流速率的影响

通过陕西长武黄土塬区的田间试验,对3个磷肥施用水平(0,90、180 kg/hm2,即F0、F1和F2)下小麦的光合性能、瞬时水分利用效率及开花期植株茎流速率的变化进行了研究,分析了不同施磷水平下小麦产量的差异,对叶片蒸腾速率和植株茎流速率做了回归分析.结果显示:不同磷肥处理下叶片净光合速率日变化均为双峰曲线,上午9时...     

井式节水灌溉下干旱区灰枣树干液流动态及其对气象因子的响应

在干旱区采用热扩散式液流仪(TDP)、HOBO小气候仪连续监测井式节水灌溉方式下盛果期枣树干液流及气象因子,探讨井式灌溉条件下盛果期枣树干液流变化对气象因子的响应。结果表明:枣树整个生育期树干液流总量为3 935 kg,夏季液流累积量为2 387 kg,约占整个生育期液流总量的61%,蒸腾耗水量夏季最为严重。影响各月枣树干液流的主导气象因子不同,而太阳辐射占各月比例较多。太阳辐射、水汽压亏缺值越大并不代表液流速率越大,液流速率的大小取决于时间、气象及枣树生理状态。     

Effects of three esca-associated fungi on Vitis vinifera L.: V. Changes in the chemical and biological profile of xylem sap from diseased cv. Sangiovese vines

A vineyard of Vitis vinifera cv. Sangiovese was surveyed for incidence of esca and xylem sap collection. Sap samples were collected from healthy vines and from those with dual infection by Phaeomoniella chlamydospora (Pch) and Togninia minima (Tmi) or triple infection by Pch, Tmi and Fomitiporia mediterranea (Fme), during each early spring in a 3-year period (2001–2003). In order to analyse the possible trends in the climatic data, temperature and rainfall were assessed. At sap harvesting, aliquots of sap were assayed for phytotoxicity and extracted with ethyl acetate for phytotoxin recovery. Moreover, the exopolysaccharide (EPS) content was evaluated on several sap samples during the bleeding period. Conidia of Pch and Tmi, mycelium of Fme and their secondary metabolites were found in the sap of the esca-affected vines, indicating that the pathogens and their by-products together with some defence substances were accumulated and then translocated. Bioactivity tests showed toxicity of the sap from esca-affected vines to healthy detached leaves of cv. Sangiovese. The daily amount of sap, the pH, and the volume (J_v) and solute (J_s) fluxes were analysed as a function of the infecting fungi. Pullulan, glucogalactomannan(s) and arabinogalactan(s) are the main EPS in the esca-infected vines, whereas in the sap of healthy vines no traces of pullulan were found. Scytalone and isosclerone usually produced in vitro by Pch and Tmi were also detected in the sap of vines infected by Pch and Tmi or by Pch, Tmi and Fme. The endogenous phytohormone content of healthy vines evaluated by the cutting bioassay was different from that of infected vines. Four phenolics belonging to three classes e.g., benzoic acid derivatives, stilbenes and flavonol-glycosides were separated and identified by HPLC.