Nucleophilic aromatic substitution reactions of chloroazines with bisulfide (HS-) and polysulfides (Sn2-)

Reactions of bisulfide and polysulfides with chloroazines (important constituents of agrochemicals and textile dyes) were examined in aqueous solution at 25 degrees C. For atrazine, rates are first-order in polysulfide concentration, and polysulfide dianions are the principal reactive nucleophiles; no measurable reaction occurs with HS-. Second-order rate constants for reactions of an array of chloroazines with polysulfides are several orders of magnitude greater than for reactions with HS-. Transformation products indicate the substitution of halogen(s) by sulfur. Ring aza nitrogens substantially enhance reactivity through a combination of inductive and mesomeric effects, and electron-withdrawing or electron-donating substituents markedly enhance or diminish reactivity, respectively. The overall second-order nature of the reaction, the products observed, and reactivity trends are all consistent with a nucleophilic aromatic substitution (S(N)Ar) mechanism. Rate constants for reactions with HS- and Sn2- (n = 2-5) correlate only weakly with lowest unoccupied molecular orbital energies, suggesting that the electrophilicity of a chloroazine is not the sole determinant of its reactivity. When second-order rate constants are extrapolated to HS- and Sn2- concentrations reported in salt marsh pore waters, half-lives of minutes to years are obtained. Polysulfides in particular could play an important role in effecting abiotic transformations of chloroazines in hypoxic marine waters.     

Nucleophilic reactions of sorbic acid

The conjugated dienoic acid structure of sorbic acid renders it susceptible to nucleophilic attack. Nucleophiles known to react with sorbic acid include sulphite ion and amines. These attack the molecule in position 5 and, in the cse of amines, cyclization to form substituted dihydropyridones may follow. Recent investigations show that thiols in general can also add to sorbic acid. Cysteine, for example, reacts slowly with sorbic acid at 80 degrees C and pH 5.5, leading to 5-substituted 3-hexenoic acid. In general, reaction products are difficult to isolate from aqueous reaction mixtures as they are susceptible to acid- and base-catalysed hydrolysis. A synthesis of model compounds may be carried out by reaction of sorbate esters with the appropriate thiol (or its ester if it is an acid) in the presence of the corresponding sodium alkoxide. It is interesting that alkyl thiols give di-adducts with sorbate ester whilst low molecular weight thiols containing an oxygen atom give a monoadduct. The mechanism of this reaction and its implications to the preparation of samples for toxicological evaluation are discussed. The reaction of sorbic acid with nitrite ion is unusual and its mechanism is considered.     

Nucleophilic aliphatic substitution reactions of propachlor,alachlor, and metolachlor with bisulfide (HS-) and polysulfides (Sn2-)

Reactions of bisulfide and polysulfides with alachlor, propachlor, and metolachlor were examined in aqueous solution to investigate the role reduced sulfur species could play in effecting abiotic transformations of chloroacetanilide herbicides. Experiments at 25 degrees C demonstrated that reactions were approximately first-order in HS- concentration and revealed that polysulfides are considerably more reactive than HS-. delta H not equal to values for reactions of the three chloroacetanilides with HS- are statistically indistinguishable at the 95% confidence level, as are delta S not equal to values, despite significant differences in second-order rate constants (kHS-). Transformation products were characterized by GC/MS (in some cases following methylation) and were found to be consistent with substitution of chlorine by the sulfur nucleophile. Products containing multiple sulfur atoms were observed for the reactions of chloroacetanilides with polysulfides, while products resulting from reaction with HS- only possessed a single sulfur atom. When second-order rate constants at 25 degrees C are multiplied by HS- and polysulfide concentrations reported in salt marsh porewaters, predicted half-lives range from minutes to hours. HS- and especially polysulfides could thus exert a substantial influence on the fate of chloroacetanilide herbicides in aquatic environments. Oxidation of the resulting sulfur-substituted products could generate ethane sulfonic acid derivatives, previously reported as prevalent chloroacetanilide degradates.     

Fate of chlorpyrifos-methyl on single wheat kernels

In the past, studies of insect development and translocation of insecticide within grain have been undertaken successfully and with demonstrated practical advantage using individual grain kernels. However, in the present study individual grain kernels treated with chlorpyrifos-methyl and stored for 7 days in open glass vials gave only 12% recovery of the insecticide. In sealed vials, part of the chlorpyrifos-methyl transferred to the inner surfaces of the vial where a significant proportion underwent degradation. The degradation product was found to be 3,5,6-trichloro-2-pyridinol, a potential grain metabolite. When 3,5,6-trichloro-2-pyridinol was applied to kernels and stored in closed vials it, too, was found to transfer on to the inner surfaces of the vials. Degradation on the container surface was prevented by using vials made from PTFE instead of glass. The concentration of chlorpyrifos-methyl applied to individual marked wheat kernels was maintained there when they were surrounded by 100 similarly treated kernels. Exchange of the insecticide occurred between the marked grain and the surrounding grain kernels even though all the kernels had been treated with the same initial quantity of chlorpyrifos-methyl.     

Studies on the atmospheric degradation of chlorpyrifos-methyl

The gas-phase atmospheric degradation of chlorpyrifos-methyl (a widely used organophosphate insecticide in Southern European regions) has been investigated at the large outdoor European Photoreactor (EUPHORE) in Valencia, Spain. Photolysis under sunlight conditions and reaction with ozone were shown to be unimportant. The rate constant for reaction of chlorpyrifos-methyl with OH radicals was measured using a conventional relative rate method with cyclohexane and n-octane employed as reference compounds with k = (4.1 ± 0.4) × 10(-11) cm(3) molecule(-1) s(-1) at 300 ± 5 K and atmospheric pressure. The available evidence indicates that tropospheric degradation of chlorpyrifos-methyl is mainly controlled by reaction with OH radicals and that the tropospheric lifetime is estimated to be around 3.5 h. Significant aerosol formation was observed following the reaction of chlorpyrifos-methyl with OH radicals, and the main carbon-containing products detected in the gas phase were chlorpyrifos-methyl oxone and 3,5,6-trichloro-2-pyridinol.     

Nucleophilic substitution of phosphorothionate ester pesticides with bisulfide (HS-) and polysulfides (S(n)2-)

The reactions of five organophosphorus insecticides (OPs) (chlorpyrifos-methyl, parathion-methyl, fenchlorphos, chlorpyrifos, and parathion) with hydrogensulfide/ bisulfide (H2S/HS-) and polysulfides (S(n)2-) were examined in well-defined aqueous solutions over a pH range from 5 to 9. The rates are first-order in the concentration of the different reduced sulfur species. Experiments at 25 degrees C demonstrated that the reaction of the five OPs with the reduced sulfur species follows a SN2 mechanism. The activation parameters of the reaction of OPs with bisulfide were determined from the measured second-order rate constants over a temperature range of 5-60 degrees C. The determined second-order rate constants show that the reaction of an OP with polysulfides is from 15 to 50 times faster than the reaction of the same OP with bisulfide. The dominant transformation products are desalkyl OPs, which indicate that the nucleophilic substitution of reduced sulfur species occurs at the carbon atom of the alkoxy groups. And also the results show that these reduced sulfur species are much better nucleophiles, and thus degrade these pesticides faster than the well-studied base hydrolysis by OH-. When the determined second-order rate constants are multiplied with the concentration of HS- and S(n)2- reported in salt marshes and porewater of sediments, predicted half-lives show that abiotic degradation by sulfide species may be of comparable importance to microbially mediated degradation in anoxic environments.     

气相色谱法测定大豆中甲基毒死蜱残留量

目的 建立气相色谱法测定大豆中甲基毒死蜱的残留量的分析方法。方法 使用乙腈萃取样品, 经中性氧化铝柱去除杂质, VF-5毛细管柱分离, 气相色谱仪定量分析甲基毒死蜱在大豆中的残留量。同时, 与SN/T 2324-2009中的方法进行对比, 考察了本方法的线性、回收率、精密度、重现性。结果 本方法中甲基毒死蜱在0.15~25.0 μg/mL范围内的线性关系良好, 曲线方程为: Y=6.6185X?0.0090, r2=0.99910, 甲基毒死蜱的检出限为0.01 mg/kg, 定量限为0.03 mg/kg, 加标回收率为89.7%~97.0%, 相对标准偏差为1.92%~5.11%。结论 与国标方法对比, 本方法灵敏度高, 定量准确, 具有简单实用、效率高、成本低等优点, 适合大豆中甲基毒死蜱残留量的检测。     

加热蒜氨酸形成活性硫产物的鉴定

为研究加热蒜氨酸后所形成的活性硫(RSS)化合物,在363.15 K温度下加热纯蒜氨酸溶液后,用液相色谱-质谱联用法(LC-MS)、串联质谱法(MS/MS)和液相色谱-高分辨质谱法(UPLC-HRMS)联用鉴定所形成的RSS产物。结果表明,蒜氨酸受热分解、转化可产生烯丙基丙氨酸基二硫烷、三硫烷和四硫烷、双丙氨酸基二硫烷、三硫烷和四硫烷等RSS化合物;其中烯丙基丙氨酸基四硫烷应是新发现的有机含硫化合物。提出了蒜氨酸加热形成RSS和生成S-烯丙基-L-半胱氨酸的新途径。结果表明,厌氧、加热蒜氨酸时,可形成多种RSS化合物;RSS化合物有助于揭示黑蒜、蒜泥、腌制蒜等大蒜加工品的生物活性与保健作用。     

Trapping reactions of reactive carbonyl species with tea polyphenols in simulated physiological conditions

The carbonyl stress that leads to the formation of advanced glycation end products (AGEs) in diabetes mellitus has drawn much attention recently. Reactive alpha-dicarbonyl compounds, such as glyoxal (GO) and methylglyoxal (MGO), have been shown to be a high potential glycation agent in vitro and in vivo. In this study, epicatechins in green tea and theaflavins in black tea were found to be able to reduce the concentration of MGO in physiological phosphate buffer conditions. Modified MGO derivatization for GC/flame ionization detector (FID) method in quantification was systematically conducted. In molar ratio of 3 (MGO/polyphenol), theaflavin-3,3'-digallate (TF3) in theaflavins and (-)-epigallocatechin (EGC) in epicatechins showed the highest MGO reduction at 66.65 and 45.74%, respectively, after 1 h of incubation. In kinetic study (molar ratio of MGO/polyphenol = 1:1), rapid MGO reduction occurred within 10 min. Identities of primary adducts between (-)-epigallocatechin gallate (EGCG) and MGO were determined. Newly generated stereoisomers at the C8 position of EGCG A-ring were isolated with a chiral column, and structurally confirmed by 2-D NMR analyses.     

Chemistry and reactions of reactive oxygen species in foods

Reactive oxygen species (ROS) are formed enzymatically, chemically, photochemically, and by irradiation of food. They are also formed by the decomposition and the inter-reactions of ROS. Hydroxy radical is the most reactive ROS, followed by singlet oxygen. Reactions of ROS with food components produce undesirable volatile compounds and carcinogens, destroy essential nutrients, and change the functionalities of proteins, lipids, and carbohydrates. Lipid oxidation by ROS produces low molecular volatile aldehydes, alcohols, and hydrocarbons. ROS causes crosslink or cleavage of proteins and produces low molecular carbonyls from carbohydrates. Vitamins are easily oxidized by ROS, especially singlet oxygen. The singlet oxygen reaction rate was the highest in ss-carotene, followed by tocopherol, riboflavin, vitamin D, and ascorbic acid.     

Use of immunological techniques for detecting species substitution in raw and smoked fish

 Immunological techniques based on double immunodiffusion and immunodotting have been designed to detect the substitution of halibut (Hippoglossus hippoglossus) for sole (Solea solea) fillets. An immunodotting technique has been also developed to differentiate between smoked cod (Gadus morhua) and smoked eel (Anguilla anguilla) fillets. Antisera raised against water-soluble extracts of raw halibut and smoked cod were employed. Antiserum to cod proteins did not show cross-reaction with eel proteins, whereas antiserum to halibut proteins cross-reacted with sole proteins. Species-specific antiserum to halibut proteins was achieved by adsorption on a polymer of sole proteins. These methods are very easy to perform and provide the basis for the development of rapid tests for detecting species substitution in fish products. Received: 18 April 1996/Revised version: 5 July 1996     

Kinetics and mechanism of degradation of dichlorvos in aqueous solutions containing reduced sulfur species

Reactions of dichlorvos with five reduced sulfur species (hydrogen sulfide, bisulfide, thiosulfate, thiophenol, and thiophenolate) were examined in well-defined anoxic aqueous solutions to investigate their role in its degradation. Reactions were monitored at varying concentrations of reduced sulfur species over pH range to obtain the second-order reaction rate constants. Experiments at 25 degrees C demonstrated that degradation of dichlorvos promoted by bisufide, thiosulfate, and thiophenolate were of much greater importance than hydrolysis under the experimental conditions in our study. In contrast, hydrogen sulfide and thiophenol were not effective in the degradation of dichlorvos. The activation parameters of the reaction of dichlorvos with bisulfide, thiosulfate, and thiophenolate were also determined from the measured second-order rate constants over a temperature range of 12-50 degrees C. The relative reactivity of the reduced sulfur species decreases in the following order: PhS- > HS- approximately equal to S2O3(2-). When the second-order rate constants at 25 degrees C are multiplied by the environmentally relevant concentration of the reduced sulfur species, predicted half-lives of dichlorvos ranged from hours to days. The results indicated that reduced sulfur species could play a very important role in the chemical fate of dichlorvos in coastal marine environments.     

Persistence of chlorpyrifos-methyl in corn silage and effects of feeding dairy cows the treated silage

Corn was sprayed in the field at dent stage of maturity with chlorpyrifos-methyl [O, O,-dimethyl O-(3, 5, 6-trichloro-2-pyridyl) phosphorothioate] at .56, 1.12, and 2.24 kg per hectare, ensiled 1 day later, and methodology for detection of residues was developed. Losses of total residues (chlorpyrifos-methyl and its pyridinol hydrolysis product) through 83 days of ensiling were equivalent to 55, 71, and 76% of that applied. Beginning 83 days post ensiling, control and treated silages were fed to 16 cows, 4 per treatment, for 42 days during which chlorpyrifos-methyl averaged .35, .87, and 1.85 ppm, and was stable. The pyridinol averaged .44, .79, and 1.75 ppm but continued to decline and during the last week of feeding averaged only 32% of that in silage fed the 1st wk. Residue intakes amounted to .009, .022, and .054 mg chlorpyrifos-methyl and .012, .020, and .051 mg of pyridinolk/g body weight and failed to affect silage intake, milk production, blood cholinesterase activity, or body weight gains. Traces of chlorpyrifos-methyl (.003 ppm or less) were only in milk from cows on the 2.24 kg treatment. Milk from all cows fed treated silage contained traces of the pyridinol (.011 ppm or less). No trace of the O-analog of chlorpyrifos-methyl was in any sample, and all milk, urine, and feces were free of residues within 1 wk after the cows were withdrawn from treated silage.     

The persistence and activity of permethrin and chlorpyrifos-methyl sprays on jute and woven polypropylene bags

To simulate the treatment of commercial bags, the persistence and biological activity on jute and woven polypropylene sheets of permethrin emulsifiable concentrate, were studied. The residues produced in wheat grains under the sprayed sheets were also determined. Residues were analysed by gas-liquid chromatography, and bioassays with Tribolium confusum Duv. on the treated materials.The insecticide residues were of shorter persistence on jute than on polypropylene sacking material. However, higher residues were found in the grain under jute than under polypropylene bags. Permethrin was found more effective for beetle control and resulted in less residue in the grain than chlorpyrifosmethyl. Polypropylene covering provided more protection to the wheat against insect and insecticide penetration as compared with jute covering.     

Degradation of naled and dichlorvos promoted by reduced sulfur species in well-defined anoxic aqueous solutions

This work examines the reaction of reduced sulfur species (e.g., bisulfide, thiosulfate, thiophenolate) with naled, a registered insecticide, in well-defined anoxic aqueous solutions at 5 degrees C. High concentrations of reduced sulfur species can occur in the porewater of sediments and in anoxic subregions of estuaries. The dominanttransformation product from the reaction of naled with reduced sulfur species is dichlorvos, which indicates that debromination is the major reaction pathway. Dichlorvos is also a registered insecticide which is more toxic than naled. The second-order rate constants for reaction of naled with bisulfide and thiophenolate at 5 degrees C are 10.2 +/- 0.4 M(-1) s(-1) and 27.3 +/- 0.9 M(-1) s(-1), respectively, while the second-order rate constant for the reaction of naled with hydrogen sulfide and thiophenol are not significantly different from zero. The second-order rate constant of the reaction of naled with thiosulfate at 5 degrees C is 5.0 +/- 0.3 M(-1) s(-1). In contrast, the second-order rate constant of the reaction of dichlorvos with bisulfide at 25 degrees C is (3.3 +/- 0.1) x 10(-3) M(-1) s(-1). The activation parameters of the reaction of naled with bisulfide were also determined from the measured second-order rate constants over a temperature range. The results indicate that reduced sulfur species can play a very important role in the transformation of naled and dichlorvos in the coastal marine environment. It can be expected that in the presence of reduced sulfur species, naled is almost immediately transformed into the more toxic dichlorvos, which has an expected half-life of 4 days to weeks.     

灯芯绒硫化染料卷染工艺

阐述了灯芯绒硫化染料染色工艺,包括染料和助剂的选用,以及染色处方.讨论了入染前和染色时的操作要点,分析了常见染色疵病的原因,并给出回修措施.     

筒子纱水溶性硫化染料染色简介

筒子纱采用水溶性硫化染料染色,其色织产品经酵素洗后具有褪色自然,层次感强,仿旧逼真的效果。采用该工艺时,前处理中的碱剂和双氧水不宜一起加料,否则会造成强力下降很多;染色时宜选用阴离子型渗透剂;硫化碱的用量要严格控制,否则会影响色牢度。     

代碱剂SM在活性染色中的应用

棉织物活性染料染色时,采用代碱剂SM作为固色剂替代纯碱,考察了碱剂用量对染色效果的影响。结果表明,代碱剂SM用量为1.6～2 g/L,约为纯碱用量的1/10,且其固色效果与纯碱相当,色光变化不明显,耐皂洗色牢度和耐摩擦色牢度较好,可有效代替传统的固色碱剂。     

Laboratory evaluation of malathion, chlorpyrifos and chlorpyrifos-methyl for use against beetles infesting stored wheat

The relative toxicities of malathion; chlorpyrifos, 0,0-diethyl 0-(3,5,6-trichloro-2-pyridyl) phosphorothioate; and chlorpyrifos-methyl, 0,0 dimethyl 0-(3,5,6-trichloro-2-pyridyl) phosphorothioate to stored product beetles were determined using an impregnated filter paper technique. Chlorpyrifos-methyl was the most toxic compound to the 5 species tested and like chlorpyrifos was equally effective against malathion resistant and susceptible strains of Tribolium. On wheat of 12% moisture content chlorpyrifos-methyl was the most effective of the 3 compounds as a protectant against Sitophilus oryzae (L.).     

Effect of surface waxes on the persistence of chlorpyrifos-methyl in apples, strawberries and grapefruits

The effects of the cuticle and epicuticular waxes of grapefruit, strawberry and apple on the photodegradation and penetration of chlorpyrifos-methyl were studied. Photodegradation experiments were conducted by exposing the insecticide to the light of a xenon lamp in the presence of a film of wax extracted from the fruit surface. The half-life of chlorpyrifos-methyl irradiated in absence of waxes was 9.6 min. The half-lives of pesticide irradiated in the presence of wax extracts of apple, grapefruit and strawberry were 83, 34 and 26 min, respectively. In penetration studies, fruit with and without wax layers were treated with an aqueous suspension of pesticide. The penetration of the pesticide from the cuticle to the pulp was measured after 24 h. Samples without wax contained a higher total amount of insecticide than those with wax. No pesticide was detected in samples of apple and grapefruit pulp. Residues were detected in all fractions of strawberry. The waxes and cuticle appear to have some effect on the photodegradation and penetration of chlorpyrifos-methyl in fruit samples.