Influence of copper on the adsorption and desorption of paraquat, diquat, and difenzoquat in vineyard acid soils

Retention of the cationic herbicides paraquat (PQ), diquat (DQ), and difenzoquat (DFQ) in two vineyard soils with a different management history and retention capacity was examined. The influence of copper on the ability of the soils to retain the herbicides was determined by comparing the results of adsorption and desorption tests on untreated and Cu-enriched soil samples, and also on soils that were previously treated with EDTA to extract native copper. The three herbicides were strongly adsorbed by both soils. Soil 1 exhibited linear adsorption isotherms for PQ and DFQ with partition coefficients, KD, of 1.28 x 103 and 1.37 x 103 L kg-1, respectively, and a Freundlich-type isotherm for DQ with a linearized partition coefficient, KD*, of 1.01 x 103 L kg-1. On the other hand, soil 2 exhibited curved isotherms and smaller KD* values (viz. 106, 418, and 28 L kg-1 for PQ, DQ, and DFQ, respectively). Using EDTA to extract copper from the soils released new sites for the herbicides to bind. The three herbicides exhibited strong hysteresis in the adsorption-desorption process. Extracting copper decreased the percent desorption of PQ and DQ; on the other hand, it decreased the affinity of DFQ for the resulting vacant adsorption sites. Similarly, competitive adsorption tests with copper and the herbicides revealed that the metal was only capable of displacing DFQ from adsorption sites. The behavior of this herbicide in the soils was consistent with a specific adsorption model. The disparate behavior of the two soils toward the herbicides was a result of the adsorption sites in soil 1 being less extensively occupied than those of soil 2 in the adsorption tests. The effect of copper on the adsorption of DFQ in the two soils was acceptably reproduced by an adsorption model involving Coulombic and specific sorption with competition from the metal.     

Simplified cleanup and gas chromatographic determination of organophosphorus pesticides in crops

A simple and efficient cleanup method for gas chromatographic determination of 23 organophosphorus pesticides in crops including onion is described. The sample was extracted with acetone. The extract was purified with coagulating solution, which contained ammonium chloride and phosphoric acid, and then filtered by suction. The filtrate was diluted with NaCl solution and reextracted with benzene. The organic layer was evaporated and injected into a gas chromatograph equipped with a flame photometric detector (FPD) and fused silica capillary columns (0.53 mm id) coated with silicone equivalent to OV-1701, OV-1, and SE-52. Onion extract, which contained FPD interferences, was cleaned up on a disposable silica cartridge. Recoveries of most organophosphorus pesticides from spiked crops: mandarin orange, tomato, spinach, sweet pepper, broccoli, lettuce, and onion at levels of 0.02-0.28 ppm, exceeded 80%, but the water-soluble pesticides dichlorvos and dimethoate gave poor recoveries in all crops; the nonpolar pesticides disulfoton, chlorpyrifos, fenthion, prothiophos, and leptophos were not recovered quantitatively in spinach, sweet pepper, broccoli, and lettuce. IBP, edifenphos, phosmet, and pyridaphenthion were not recovered from onion because of adsorption to the silica cartridge. The detection limits ranged from 1.25 to 17.5 ppb on a crop basis.     

Liquid chromatographic determination of miconazole nitrate in creams and suppositories

A rapid method has been developed for the determination of miconazole nitrate in creams and suppositories. The sample is dissolved in ethanol, diluted in acetonitrile-water (1 + 1), and injected onto a C18 column. The mobile phase consists of 55% acetonitrile, a triethylammonium phosphate buffer, and an ion-pairing agent. The total run time is less than 4 min, and the active ingredient is determined using absorbance detection at 214 nm. The mean recovery of miconazole from spiked placebo samples was 99.7 +/- 0.7% for the cream samples at the 2% level and 98.8 +/- 0.3% for the suppository samples at the 4% level.     

覆膜对有机物料的腐解及土壤有机质特性的影响

砂滤管长期培养试验结果表明,有机物料和农肥施入土壤后,腐解残留率(Yt)与有机物料施入后的时间(t)遵循Yt=Y^λ.t_oe方程式,式中Yo为有机物料缓分解成分的碳理占加入总碳量的百分数,λ为缓解成分的分解速率。覆膜使Yt和Yo值明显降低。田间试验结果表明,覆膜降低了有机质的活性,使PQ值(胡敏酸占可提取腐殖酸的百分数)和A2/A3比值(胡敏酸在波长200nm和300nm处吸光度之比)增高,胡敏酸对光吸收增强。     

Ion-pairing liquid chromatographic determination of benzimidazole fungicides in foods

A method is described for determining residues in foods of thiabendazole, thiophanate methyl, the di-oxygen analogue metabolite [dimethyl 4,4'-O-phenylene bis (allophanate)] that is the metabolite name of the latter, and methyl-2-benzimidazole carbamate, which is the major metabolite and fungitoxic principle common to both thiophanate methyl and benomyl. The residues are extracted from the product using methanol and are partitioned into dichloromethane after initial acidification and again after subsequent alkalinization of the extract. Residues are separated and quantified by reverse-phase liquid chromatography using an ion-pairing mobile phase with UV and fluorescence detectors in tandem. Recoveries from 7 different food crops fortified at 0.2-35 ppm levels ranged from 64 to 105%.     

Improved separation method for highly purified lutein from Chlorella powder using jet mill and flash column chromatography on silica gel

We investigated an improved method for the separation of high-purified lutein from a commercially available spray-dried Chlorella powder (CP) using fine grinding by jet mill and flash column chromatography on a silica gel. Saponification and extraction of lutein were enhanced 2.3-2.9-fold in jet mill-treated CP (mean particle size, 20 microm) as compared to untreated CP (mean particle size, 67 microm). The carotenoid extract was dissolved in ether-hexane (1:1 v/v) and subjected to flash column chromatography on silica gel. A mixture of alpha- and beta-carotene was eluted with hexane, followed by elution with hexane-acetone-chloroform (7:2:1 v/v). Lutein (dark-orange band) was collected after the elution of an unknown colorless compound (detected based on UV absorbance). The purity of lutein in this fraction was over 99%, and the yield was 60%. The present study provides key information for obtaining highly purified lutein using flash column chromatography on a silica gel.     

Separation of rotenoids and the determination of rotenone in pesticide formulations by high-performance liquid chromatography.

The rotenoids deguelin, B-dihydrorotenone, dehydrorotenone, rotenone, 6alpha beta, 12alpha beta-rotenolone, and tephrosin were chromatographed on 8-12 mum silica. A mobile phase of chloroform-isooctane (35+65) pumped at a flow rate of 1 ml/min through a 30 cm column was used and the absorbance of the eluate was monitored at 294 nm. Rotenone, B-dihydrorotenone, deguelin, and dehydrorotenone are completely resolved while 6alpha beta, 12alpha beta-rotenolone and tephrosin chromatograph as one peak. This method has potential as a preparative separation technique for rotenoids. Also described is a procedure to quantitatively measure rotenone in pesticide formulations. Samples were extracted with chloroform and chromatographed at a flow of 2.5 ml/min. The method is rapid (rotenone is eluted in 12 min) and reproducible.     

有机物料对不同作物根系土壤腐殖质组成和结构的影响

为探讨施用有机物料后不同作物根系土壤腐殖质各组分含量和胡敏酸元素组成的变化情况,以吉林农业大学试验田培肥2a的黑土为研究对象,试验选取3种作物(玉米、大豆、白菜),每种作物设4种施肥处理,包括化肥(CK)、玉米秸秆配施化肥、树叶配施化肥和鸡粪配施化肥。采用腐殖质修改法提取水溶性物质(WSS)、胡敏酸(HA)、富里酸(FA)、胡敏素(HM),利用重铬酸钾外加热法测定腐殖质各组分有机碳含量,采用分光光度计法测定HA和FA的光学性质,通过光密度E_4/E_6值和元素组成分析HA的结构变化。结果表明:土壤总有机碳(TOC)和腐殖质各组分有机碳含量均表现为白菜玉米大豆。相比CK,配施有机物料后作物根系土壤TOC、WSS、HA含量分别显著增加5%~8%,34%~55%,8%~20%,FA含量变化不明显。相比树叶和鸡粪,秸秆可显著提高TOC含量;WSS在各物料之间差异不明显;HM含量表现为秸秆树叶鸡粪CK。有机物料对PQ值的影响因作物而异,秸秆和鸡粪对玉米、大豆根系土壤PQ值(HA占腐殖酸的比率)的影响相似,而鸡粪对白菜根系土壤PQ值的影响显著高于玉米秸秆。施用有机物料后HA的E_4/E_6未发生明显改变,FA的E_4/E_6显著提高。有机物料使根系土壤HA缩合度升高,分子结构更加复杂,且有利于HA含氮基团的形成,以秸秆处理作用最好。由此可见,有机物料具有良好的培肥效果,其中鸡粪对白菜根系土壤培肥效果最显著,秸秆与鸡粪对玉米、大豆根系土壤培肥效果相似,均显著高于化肥。     

High pressure liquid chromatographic determination of polynuclear aromatic hydrocarbons in oysters.

A high pressure liquid chromatographic (HPLC) procedure is described for determining 13 polynuclear aromatic hydrocarbon (PNA) compounds in oysters at the 2 ppb level. These compounds are extracted from shellfish with acetonitrile and partitioned into petroleum ether; the petroleum ether is removed and the residue is saponified. The aromatic compounds are isolated by passing the saponifeid residue through silica gel and further purified and fractionated by muStyragel gel permeation chromatography. The in-ividual PNAs are then quantitatively determined by using a reverse phase HPLC column coupled to fluorescence, spectrophotometric, and 254 nm absorbance detectors in series. Recoveries from spiked samples generally were greater than 80%.     

Fast and simple liquid chromatographic determination of nonphosphorylated thiamine in infant formula, milk, and other foods

A very fast and simple method for determination of nonphosphorylated thiamine in infant formula products, milk, and other nonfortified foods using reverse-phase ion-pairing liquid chromatography (LC) has been developed. Sample preparation consists of merely acid treatment to precipitate protein, followed by gravity filtration. No concentration, extraction, derivatization, or preliminary column cleanup is necessary. The chromatography is done on muBondapack C18 with an aqueous mobile phase containing 0.15% sodium hexane sulfonate, 20% MeOH, 1.5% HOAc, and 0.1% EDTA at a flow rate of 2.5 mL/min. Ultraviolet detection at 248 nm is used. A typical run takes 7 min, and 60 samples can be processed in 4 h. Results average from 96 to 104% of theory for the infant formula products analyzed. A 99 to 103% recovery of spike has been demonstrated. Method precision is good (2 to 4% RSD, short-term, and 2 to 5% RSD, long-term, depending on sample type). Peak separation from thiamine phosphate esters is achieved. Specificity is demonstrated by UV spectral scan and absorbance ratios. Equivalency to a microbial method (validated against the official AOAC fluorometric method) was established. The method is used for high-volume quality control testing of milk-based infant formula products in the ready-to-use, concentrate, or powder form.     

Determination of quinomethionate (6-methylquinoline-2,3-diyldithiocarbonate) residues in crops by in situ fluorometry.

A simple method is described for the quantitative determination of quinomethionate (6-methylquinoline- 2,3 - diyldithiocarbonate) in crops. The pesticide residue is extracted with acetonitrile and partitioned in petroleum ether. After separation from the co-extractives by thin layer chromatography (TLC), the fluorescence is measured directly on a silica gel TLC plate. An average of 89% recovery is obtained at the 0.05 ppm level in apples, peaches, pears, and tomatoes.     

Reversible precipitation of casein micelles with a cationic hydroxyethylcellulose

The cationic hydroxyethylcellulose Polyquaternium 10 (PQ10) was found to produce a dose-dependent destabilization of casein micelles from whole or skim milk without affecting the stability of most of the whey proteins. The anionic phosphate residues on caseins were not determinant in the observed interaction since the destabilization was also observed with dephosphorylated caseins to the same extent. However, the precipitation process was completely inhibited by rising NaCl concentration, indicating an important role of electrostatic interactions. Furthermore, the addition of 150 mM NaCl solubilized preformed PQ10-casein complexes, rendering a stable casein suspension without a disruption of the internal micellar structure as determined by dynamic light scattering. This casein preparation was found to contain most of the Ca2+ and only 10% of the lactose originally present in milk and remained as a stable suspension for at least 4 months at 4 degrees C. The final concentration of PQ10 determined both the size of the casein-polymer aggregates and the amount of milkfat that coprecipitates. The presence of PQ10 in the aggregates did not inhibit the activity of rennet or gastrointestinal proteases and lipases, nor did it affect the growth of several fermentative bacteria. The cationic cellulose PQ10 may cause a reversible electrostatic precipitation of casein micelles without disrupting their internal structure. The reversibility of the interaction described opens the possibility of using this cationic polysaccharide to concentrate and resuspend casein micelles from whole or skim milk in the production of new fiber-enriched lactose-reduced calcium-caseinate dairy products.     

Spectrophotometric determination of silicon in soil solutions by flow injection analysis: Reduction of phosphate interference

Abstract

A flow injection analysis (FIA) procedure for the determination of dissolved silica (0.04–20 mg/L Si) in aqueous solution has been optimized to reduce phosphate interference. Determinations are based on measurement of absorbance at 790 nm of heteropoly molybdenum blue formed by reduction with ascorbic acid at room temperature. Phosphate did not interfere in a 15‐fold excess. The optimized procedure was tested on soil solutions isolated by centrifugation of various horizons from a Typic Haplohumod. Si concentrations of 1.3–4.8 mg/L Si were found with a variation coefficient of about 2. Results obtained compared well with those obtained by a manual reference method and a proprietary FIA method except in solutions high in dissolved humic material where slightly higher values were obtained by the optimized method. In a standard addition mode the optimized method yielded 5–15% lower values than in the ordinary mode. This difference was reduced by persulfate oxidation of organic matter. Soil solutions investigated were very low in phosphate but phosphate spiking experiments demonstrated that phosphate interference was less than in model solutions matched in metal ion concentrations and insignificant in solutions low in humic material and with less than 10 mg/L P. Dissolved silica was unstable in a solution isolated from an organic horizon of high biological activity.     

Paraquat detoxification with p-sulfonatocalix-[4]arene by a pharmacokinetic study

The p-sulfonatocalix[n]arenes are supposed to show potential application in the clinical treatment of viologen poisoning. In the present study, p-sulfonatocalix[4]arene (C4AS), the most common derivative of p-sulfonatocalix[n]arenes, is used to study the antidotic mechanism for paraquat (PQ) by pharmacokinetics in vivo. A high-performance liquid chromatography (HPLC) method was established to determine the concentration of PQ in rat plasma. The results showed that the peak plasma concentration (C(max)) and area under the plasma concentration-time curve (AUC(0-t)) were significantly lower after C4AS intervention than in the PQ intoxication group. It was considered that C4AS has great effective detoxication to PQ poisoning, and the results of in vitro intestinal absorption studies showed that C4AS can inhibit the absorption of PQ via oral administration by forming a stable inclusion constant.     

Photosynthetic Response of Maize Plants Against Cadmium and Paraquat Impact

The effects of cadmium (Cd) and/or paraquat (PQ) toxicity on photosynthesis in maize leaves were examined by measurement of gas exchange and chlorophyll content in hydroponically cultured plants. It was found that growth rate was distinctly influenced only by 100 µM Cd treatment. Chlorophyll a and chlorophyll b decreased along with the increase of Cd concentration, while PQ spraying, alone and combined with Cd, increased chlorophyll a content on the third and seventh experimental days. Generally, carotenoid content increased in response to Cd and PQ and reached the highest levels at 100 µM Cd. Rate of photosynthesis in maize decreased after Cd treatment. CO₂ assimilation was approximately 60% reduced at 50 µM Cd and 70% reduced in the presence of 100 µM Cd. PQ toxicity was partly overcome after the third day of exposure. Transpiration and stomatal conductance in maize leaves decreased on the third day along with Cd concentration and PQ spraying, except for the 25-µM Cd-treated plants. On the tenth day, the 25-µM Cd-treated plants and those from PQ-treated variants showed an increase of transpiration and stomatal conductance. Maize exhibited an ability to accumulate Cd in high quantities, especially in the roots—over 4,500 mg Cd/kg dry weight.     

A new test method for the evaluation of total antioxidant activity of herbal products

A new test method for measuring the antioxidant power of herbal products, based on solid-phase spectrophotometry using tetrabenzo-[b,f,j,n][1,5,9,13]-tetraazacyclohexadecine-Cu(II) complex immobilized on silica gel, is proposed. The absorbance of the modified sorbent (lambda(max) = 712 nm) increases proportionally to the total antioxidant activity of the sample solution. The method represents an attractive alternative to the mostly used radical scavenging capacity assays, because they generally require complex long-lasting stages to be carried out. The proposed test method is simple ("drop and measure" procedure is applied), rapid (10 min/sample), requires only the monitoring of time and absorbance, and provides good statistical parameters (s(r)相似文献   

Antioxidative activity and active components of longan (Dimocarpus longan Lour.) flower extracts

Three different solvent extracts (methanol, ethyl acetate, and n-hexane) of longan ( Dimocarpus longan Lour.) flowers were assayed with three different antioxidant capacity methods, namely, the DPPH free radical scavenging effect, the oxygen radical absorbance capacity (ORAC) assay, and the inhibition of Cu(2+)-induced oxidation of human low-density lipoprotein (LDL). It was revealed that the methanol extract has the best antioxidative activity, followed by ethyl acetate and n-hexane extracts. The methanol extract was separated by liquid-liquid partition into n-hexane, ethyl acetate, n-butanol, and water fractions. The ethyl acetate fraction was found to have the highest activity of delaying LDL oxidation. After silica gel column chromatography, the fraction having a superior activity was identified as containing two major compounds, (-)-epicatechin and proanthocyanidin A2.     

Pseudomonas putida improved soil enzyme activity and growth of kasumbha under low input of mineral fertilizers

Effective management of the nutrients and enzyme activity in the soil is necessary for maximum crop growth and productivity. However, the excessive use of chemical fertilizers (CFs) not only adversely affects the soil nutrient status and soil physicochemical properties but also aids pollution to the ecosystem. The objective of present study was to investigate the effect of single as well as combined applications of phosphate-solubilizing bacteria and agrochemicals on important soil enzyme activities and their impact on the growth of kasumbha (safflower). Pseudomonas putida (P. putida;10⁶ cells/mL) was applied as seed inoculation prior to sowing, and CFs were applied as full, half, and quarter doses during sowing to modulate the growth of kasumbha host plants. P. putida in combination with half dose of CFs (PH) increased the soil urease and phosphatase activities, while P. putida combined with quarter dose of CFs (PQ) augmented the soil invertase activities. Moreover, the PQ treatment exhibited the maximum colony-forming units of P. putida. Leaf chlorophyll, carotenoids, protein contents, and root lengths were increased by PH treatment. Whereas, shoot length and leaf area were improved by PH and PQ treatments, respectively. Leaf protease activity was enhanced by P. putida in combination with full dose of CFs and PQ treatments, while leaf phosphate contents were significantly improved by PQ treatment. It can be concluded that P. putida in combination with half as well as quarter doses of CFs is a promising approach for the improvement of soil enzyme activities and growth of kasumbha and replacing 50% of the use of CFs.     

化学因子对膜脂组分的影响与诱导抗病作用的关系

本研究结果表明 ,抗病品种余水糯O ·2 含量和MDA含量比感病品种浙辐 80 2高 ,而CAT活性和POD活性则相反。PQ处理使两品种产生系统抗性的同时 ,也使处理叶中CAT活性、POD活性及MDA含量升高。这种变化从 2 4h开始 ,在 48～ 72h达较高水平。余水糯和浙辐80 2处理叶中平均CAT活性分别升高 1 6 5 %和 1 1 3 % ,平均POD活性分别升高 37 2 %和2 5 3 % ,平均MDA含量分别升高 38 5 %和 32 2 %。PQ处理后第 3天 ,浙辐 80 2处理叶中膜脂酸相对含量变化较大 ,饱和脂肪酸增加 1 1 8% ,IUFA降低 7 5 % ,IUFA降低主要是由亚麻酸 ( 1 8∶3)含量减少所致。Trion使PQ对处理叶中各指标的影响及对XOO76 2 5的诱导抗病作用减弱     

Determination of 4(5)-methylimidazole in soy sauce and other foods by LC-MS/MS after solid-phase extraction

A method for the determination of 4(5)-methylimidazole (4MeI) in naturally brewed soy sauce was developed for the first time using solid-phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS). SPE on silica-based reversed-phase cartridges with heptafluorobutyric acid as an ion-pairing reagent was used for the efficient cleanup of 4MeI. A multimode ODS column was employed for the chromatographic separation. To subtract the matrix effect during LC-MS/MS analysis, a standard addition method was used. The levels of 4MeI found in naturally brewed soy sauce were extremely low (ranging from <0.002 to 0.023 μg/g), whereas those in soy sauces containing caramel color were generally high (ranging from 0.43 to 4.8 μg/g). The method proved to be useful for the analysis of 4MeI in other foods such as caramel colors, drinks, and Worcestershire sauce.