Application of reverse-phase h.p.l.c. for the determination of partition coefficients

Reverse-phase high performance liquid chromatography (h.p.l.c.), using a C₁₈ analytical column, has been applied to the determination of partition coefficients for a range of agrochemicals and industrial chemicals. Using a correlation plot of the logarithm of the capacity factor (k) with the logarithm of the n-octanol/water partition coefficient (P_ow), partition coefficients were predicted with a 95% tolerance interval of ± log 0.80 of the literature ‘shake flask’ value for compounds of random structure over the log P_ow range 0–6. Individual regression lines were fitted for compounds of comparable size and functional grouping, which reduced any bias and thereby enabled more accurate predictions to be made. The reverse-phase h.p.l.c. method has a number of advantages over the traditional ‘shake-flask’ method. Quantitative methods are not required or do not have to be developed and only the determination of the retention time is necessary. Quick and precise determinations of retention times are facilitated by h.p.l.c. and further improvement can be obtained by automation of solvent mixing, solute injection and data processing. H.p.l.c. was used to generate partition coefficient data for highly hydrophobic materials and, because of its resolving power, data for mixtures and solvent fractions. Dual detection, using u.v. and r.i. in series, was necessary for some compounds, particularly unknown mixtures and impure compounds. Calculations of log P_ow based on the fragment-addition method using the structural data file, MACCS, was of considerable value in confirming experimentally derived values. In certain cases, calculated log P_ow values were considered more trustworthy than experimental values.     

梭梭幼苗根系分泌物提取方法的研究

为了探讨梭梭根系分泌物中的化学成分,本文采用水浸提取和循环灌溉两种方法对梭梭幼苗根系分泌物进行收集和提取,结合气相色谱-质谱联用分析技术,分析梭梭幼苗根系分泌物中组分和含量的差异。实验结果表明:循环灌溉收集的梭梭幼苗根系分泌物中检测到35种化合物,包括酚醌类、醛酮类、醇类、酸类、脂类和胺类化合物;硅烷化处理后,主要增加部分强极性有机酸,如苯甲酸。水浸提取梭梭幼苗根系分泌物的中性相组分共检测出27种化合物,但未检测到酚醌类化合物;碱性相组分共检测出23种化合物,醛酮类化合物种类减少,烷烃类化合物种类增加;酸性相组分中仅检测到10种化合物,以醇类化合物为主,占检出化合物总量的72.62%。收集梭梭幼苗根系分泌物循环灌溉是一种有效的方法。     

Fate of chlorsulfuron in the environment. 1. Laboratory evaluations

The behaviour and fate of chlorsulfuron in aqueous and soil systems were examined in laboratory studies. Aqueous hydrolysis was pH-dependent and followed pseudo-first-order degradation kinetics at 25°C, with faster hydrolysis occurring at pH 5 (half-life 24 days) than at either pH 7 or 9 (half-lives >365 days). Degradation occurred primarily by cleavage of the sulfonylurea bridge to form the major metabolites chlorobenzenesulfonamide (2-chlorobenzenesulfonamide) and triazine amine (4-methoxy-6-methyl-1,3,5-triazin-2-amine). This route is a major degradation pathway in water and soil systems. Aqueous photolysis (corrected for hydrolysis) proceeded much more slowly (half-life 198 days) than aqueous hydrolysis and is not expected to contribute significantly to overall degradation. Hydrolysis in soil thin-layer plates exposed to light (half-life 80 days), however, progressed at a much faster rate than in dark controls (half life 130 days), which suggests that a mechanism other than direct photolysis may have been operative. An aerobic soil metabolism study (25°C) in a Keyport silt loam soil (pH 6·4, 2·8% OM) showed that degradation was rapid (half-life 20 days). Dissipation in an anaerobic sediment/water system (initial pH of water phase 6·7, final pH 7·4) progressed much more slowly (half-life >365 days) than in aerobic soil systems. Major degradation products in aerobic soil included the chlorobenzenesulfonamide and triazine amine as in the aqueous hydrolysis study. Neither of these degradation products exhibited phytotoxicity to a variety of crop and weed species in a glasshouse experiment, and both exhibited an acute toxicological profile similar to that of chlorsulfuron in a battery of standard tests. Demethylation of the 4-methoxy group on the triazine moiety and subsequent cleavage of the triazine ring is another pathway found in both aqueous solution and soils, though different bonds on the triazine amine appear to be cleaved in the two systems. Hydroxylation of the benzenesulfonamide moiety is a minor degradation pathway found in soils. Two soils amended with 0·1 and 1·0 mg kg^-1 chlorsulfuron showed slight stimulation of nitrification. The 1·0 mg kg^-1 concentration of chlorsulfuron resulted in minor stimulation and inhibition of ¹⁴C-cellulose and ¹⁴C-protein degradation, respectively, in the same soils. Batch equilibrium adsorption studies conducted on four soils showed that adsorption was low in this system (K_oc 13–54). Soil thin-layer chromatography of chlorsulfuron (R_f=0·55–0·86) and its major degradation products demonstrated that the chlorobenzenesulfonamide (R_f=0·34–0·68) had slightly less mobility and that the triazine amine (R_f=0·035–0·40) was much less mobile than chlorsulfuron. In an aged column leaching study, subsamples of a Fallsington sandy loam (pH_water 5·6, OM 1·4%) or a Flanagan silt loam (pH_water 6·4, OM 4·0%) were treated with chlorsulfuron, aged moist for 30 days in a glasshouse and then placed upon a prewet column of the same soil type prior to initiation of leaching. This treatment resulted in the retention of much more total radioactivity (including degradation products) than by a prewet column, where initiation of leaching began immediately after chlorsulfuron application, without aging (primarily chlorsulfuron parent). © 1998 SCI     

马铃薯病毒及其检疫重要性初析

本文列举了马铃薯上发生的２０多种病毒以及有关马铃薯病毒在我国的发生情况，分析了马铃薯Ａ病毒及马铃薯帚顶病毒的危险性及其检疫重要性。     

Variation in the resistance of barley cultivars and in the pathogenicity of Drechslera teres f. sp. maculata and D. teres f. sp. teres isolates from France

Isolates of Drechslera teres that cause net or spot-type symptoms on barley ( Hordeum vulgare ) were collected in 1986 and 1987 from fields in different regions of France. Variations in pathogenicity were evaluated using 12 barley cultivars. The Middle-Eastern cultivars Arrivate and 79-S10-10 were resistant to all isolates except R5 and S5. The Ethiopian cultivar C1 5791, previously reported to be resistant, was susceptible to the R5 and S5 biotypes. There was a high correlation coefficient between the classification of cultivars for resistance to D. teres f. sp. teres and D. teres f. sp. maculata. A method for conserving the virulence of the isolates on straw is evaluated. The virulence level of the isolates was the same after 4 years of storage using this method.     

Identification of the photochemical decomposition product of chlorothalonil by 13C n.m.r. spectroscopy

The light-induced decomposition of chlorothalonil (2,4,5,6-tetrachloroisophthalonitrile) in benzene and toluene was found to give rise to one and three products respectively. These were shown by gas chromatography-mass spectrometry to be trichlorodicyanobiphenyls and the benzene adduct was fully identified by ¹³C n.m.r. spectroscopy as 2,4-dicyano-3,5,6-trichlorobiphenyl.     

Studies on the breakdown of p-chlorophenyl methylcarbamate. I. In soil

The compound p-chlorophenyl methylcarbamate (PCMC) was shown to inhibit the breakdown of the herbicide isopropyl 3-chlorophenylcarbamate (chlorpropham) in soil, increasing its half-life from 7.5 to 20 days. The inhibitory effect of PCMC on the breakdown of chlorpropham persisted for 40 days, with a half-life of 20 days. The conversion in soil, of PCMC to p-chlorophenol, a compound which did not affect the persistence of chlorpropham, was demonstrated, and it is suggested that spontaneous chemical hydrolysis may account for this conversion. PCMC and p-chlorophenol were shown to be of low toxicity to buckwheat (Fagopyrum esculentum Moensch.).     

Reductive detoxification of the acetophenone skeleton of the carnation phytoanticipin by Fusarium oxysporum f.sp. dianthi

The skeleton of the carnation phytoanticipin, acetophenone, was detoxified by Fusarium oxysporum f.sp. dianthi , the main fungal parasite of carnation. This process consisted of the reduction to ethanol of the acetyl group, leading to the formation of phenylethanol, which has lower fungitoxic activity than the parent molecule. The conversion took place through the activity of an adaptive fungal oxidoreductase, which was NADH-dependent and was released by the fungus as two enzymatic forms within the culture substrate in the presence of acetophenone. Reduction was stereospecific and gave rise to only one of the two possible enantiomeric forms.     

苏云金杆菌对棉铃虫代谢影响研究

以低剂量苏云杆菌（Ｂａｃｉｌｌｕｓｔｈｕｒｉｎｇｅｎｓｉｓｖａｒ．ｋｕｒｓｔａｋｉ）饲喂棉铃虫（Ｈｅｌｉｏｔｈｉｓａｒｍｉｇｅｒａ）三龄幼虫，定期测定幼虫的部分生理指标，结果发现：幼虫肠液，体液ｐＨ值，血细胞数量，血液蛋白含量，虫体脂肪含量均发生明显变化。     

Studies on the breakdown of p-chlorophenyl methylcarbamate. II. In cultures of a soil Arthrobacter sp.

p-Chlorophenyl methylcarbamate (PCMC) underwent spontaneous hydrolysis in aqueous solution to p-chlorophenol with concomitant loss of ability to inhibit hydrolysis of the phenylcarbamate isopropyl phenylcarbamate (propham). A phenylcarbamate-degrading soil Arthrobacter sp. had no direct effect on PCMC itself but formed 4-chlorocatechol during the metabolism of p-chlorophenol.     

Survey of cereal diseases and petts in the Netherlands. 5. Occurrence of Septoria spp. in winter wheat

Data of the annual surveys of circa 100 commerical winter wheat fields were compiled to describe epidemics ofSeptoria spp. in the Netherlands during 1974–1986. In May, during the first node stage,S. tritici was dominant whileS. nodorum was virtually absent. In July, during ripening,S. tritici on average dominated overS. nodorum, though in the most continental districts of the countryS. nodorum predominated.In May between 1974 and 1984, on average 56% of the fields showed leaf infections bySeptoria spp., while in July between 1975 and 1986, on average 83% of the fields showed leaf infections. Prevalence ofSeptoria spp. has increased during the surveys. Annual intensity ofSeptoria spp. in winter wheat crops was positively correlated with precipitation and negatively with average monthly sunshine duration during the harvest-month August of the previous growing season. The correlation with sunshine during August could indicate that ascospores play a major role in subsequent epidemics; but whether it is a causal relation remains to be answered.Present address: Center for Agrobiological Research (CABO-DLO), PO Box 14, 6700 AA Wageningen, the Netherlands     

Effect of mixed inoculations with Fusarium oxysporum f. sp. lycopersici and F. oxysporum f. sp. dianthi on the phenols content of tomato plants

Forms ofFusarium oxysporum specific on hosts other than tomato induce in this plant greater initial increases of the phenols content than the pathogenic f. sp.lycopersici. Mixed inoculations of f. sp.lycopersici and f. sp.dianthi are on the contrary no more effective in inducing the phenol accumulation 24 h after the infection than f. sp.lycopersici alone. This observation suggests that the pathogen can suppress the phenolic response that is typical of the incompatible combinations.Samenvatting Vormen vanFusarium oxysporum welke pathogeen zijn voor andere planten dan de tomaat induceren in deze plant aanvankelijk een grotere toename van het fenolgehalte dan de pathogene f. sp.lycopersici. Inoculaties met een gemengd inoculum van de f. sp.lycopersici en f. sp.dianthi hebben daarentegen geen groter effect op de toename van het fenolgehalte 24 uur na infectie dan de inoculaties met f. sp.lycopersici alleen. Verondersteld wordt dat het pathogeen de toename van het fenolgehalte, dat typerend is voor de incompatibele combinatie, kan onderdrukken.     

柑桔病毒类有害生物及其检疫重要性

本文针对柑桔上发生的数十种病毒类有害生物，列举了具有明确分类地位的６种病毒、５种类病毒、１种类菌原体及１种类细菌，初步分析了其所引起的柑桔病害的危险性及其检疫重要性     

公元600-2000年宝鸡地区洪涝灾害发生规律

通过对历史文献资料的搜集和整理,对公元600-2000年宝鸡地区洪涝灾害变化阶段、趋势、等级分布和成因进行了研究。结果表明：宝鸡地区洪涝灾害可划分为轻度涝灾、中度涝灾、大涝灾、特大涝灾4级,以中度和大涝灾为主,占灾害记录总数的71.55%,特大洪涝灾害发生较少,占灾害记录总数的8.94%。公元600-2000年的1 400 a可以分为14个洪涝灾害发生阶段: 10、11、12、13、14、15世纪为无洪涝灾害或极少洪涝灾害发生阶段,7、8、9、16、17、18、19、20世纪为洪涝灾害多发阶段。洪涝灾害发生频次具有空间差异,9个县区由多到少依次为：宝鸡、扶风、千阳、凤翔、凤县、陇县、麟游、岐山、眉县。最多与最少之间相差26次,空间差异较大。洪灾集中于夏、秋两季。宝鸡地区洪涝灾害的发生主要是由地理位置、降水和气候异常波动以及人类活动综合因素影响的结果。     

Contribution to the taxonomy and pathogenicity of fungicolous Verticillium species. II. Pathogenicity

In recent years in the Netherlands a second mushroom species,Agaricus bitorquis, which prefers higher temperatures thanA. bisporus and is less susceptible to certain diseases, is often commercially grown.Verticillium fungicola var.fungicola, the causal agent of dry bubble, is responsible for considerable damage in crops ofA. bisporus. InA. bitorquis, however, dry bubble has hardly been noticed, but brown spots due toV. fungicola var.aleophilum resulted in inferior mushroom quality. The latter variety also caused brown spots ina. bisporus, but to a minor degree. In variety Les Miz 60 ofA. bisporus, however, it also induced fruit-body deformation in a way different from dry bubble. Verticillium psalliotae, isolated fromA. bitorquis in England, induced more confluent brown spots inA. bitorquis. In the netherlands, where moreA. bitorquis is grown than in other countries,V. psalliotae has not yet been encountered in crops ofA. bitorquis. V. psalliotae, which has a high temperature optimum for mycelial growth, likeV. fungicola var.aleophilum andA. bitorquis, did not infectA. bisporus in our trials.Artificial infection ofA. bisporus orA. bitorquis could not be accomplished with the following related and/or fungicolous fungi:Verticillium lamellicola, V. fungicola var.flavidum, V. biguttatum, Nectriopsis tubariicola, Acremonium crotocinigenum andAphanocladium album.Samenvatting Vooral in Nederland wordt sinds een aantal jaren naastAgaricus bisporus ook de warmteminnende champignonsoortAgaricus bitorquis geteeld, die minder vatbaar is voor bepaalde ziekten. TerwijlVerticillium fungicola varfungicola in de teelt vanA. bisporus droge mollen en daardoor veel schade veroorzaakt, komen in de teelt vanA. bitorquis geen droge mollen voor maar wel bruine vlekken, die tot kwaliteitsverlies en dus schade leiden. De vlekken bleken veroorzaakt te worden doorV. fungicola var.aleophilum. Deze schimmel veroorzaakte ook inA. bisporus bruine vlekken, hoewel in minder ernstige mate, maar in het ras Les Miz 60 vanA. bisporus bovendien misvormde champignons, die wel op droge mollen leken, maar daaraan niet gelijk waren.OokV. psalliotae, in Engeland geïsoleerd vanA. bitorquis met vlekken, veroorzaakte wat meer samenvloeiende, bruine vlekken inA. bitorquis. In Nederland, waar meerA. bitorquis geteeld wordt dan in andere landen, isV. psalliotae nog niet aangetroffen in teelten vanA. bitorquis. InA. bisporus kon geen kunstmatige infectie worden verkregen metV. psalliotae, die net alsV. fungicola var.aleophilum enA. bitorquis warmteminnend genoemd zou kunnen worden.Met de volgendeVerticillium-achtige of van paddestoelen geïsoleerde schimmels kon evenmin op kunstmatige wijze een infectie worden opgeroepen inA. bisporus ofA. bitorquis: Verticillium lamellicola, V. fungicola var.flavidum, V. biguttatum, Nectriopsis tubariicola, Acremonium crotocinigenum enAphanocladium album.