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1.
A study is made of the kinetics and mechanism of the reaction of radiolytically produced hydrated electron (e-(aq)) with some triazine derivatives [1,3,5-triazine (T), 2,4,6-trimethoxy-1,3,5-triazine (TMT), 2,4-dioxohexahydro-1,3,5-triazine (DHT), 6-chloro N-ethyl N-(1-methylethyl)-1,3,5-triazine 2,4-diamine (atrazine, AT), and cyanuric acid (CA)] in aqueous medium using pulse and steady-state radiolysis techniques. The second-order rate constants were determined from the pseudo first-order decay of e(-)(aq) in the presence of triazines at 720 nm, and the values obtained with T, TMT, AT, and CA are in the order of 10(9) dm(3) mol(-1) s(-1) and that of DHT was 10(8) dm(3) mol(-1) s(-1) at pH 6. The transient absorption spectra from the reaction of e(-)(aq) with T and TMT are characterized by their lambda(max) at 310 nm, and those of DHT and CA are around 280 and 290 nm, respectively. However, a very weak and featureless absorption spectrum is obtained from AT. On the basis of the spectral evidence and on the quantitative electron transfer from the transient intermediates to the oxidant, methyl viologen (MV(2+)), the intermediate radicals are assigned to N-protonated electron adducts (with the unpaired spin density at carbon) of triazines. The degradation profiles, monitored as the disappearance of parent triazine concentrations as a function of dose, obtained with AT, TMT, CA, and DHT, highlight the potential use of e-(aq) in the degradation of triazines.  相似文献   

2.
Oxidative reaction between hydroxymethyl radical ((*)CH(2)OH) and kaempferol, in methanol and methanol/water mixtures, was studied by gamma-radiolysis using a (60)Co source. Radiolysis was performed with concentrations and doses ranging from 5 x 10(-)(5) M to 5 x 10(-)(3) M and from 0.5 kGy to 14 kGy, respectively. Kaempferol degradation was followed by HPLC. Results showed that (*)CH(2)OH reacts with kaempferol at the 3-OH group and produces two depsides (K1 and K2) and other products including K3. K1, K2, and K3 were identified by NMR, LC-MS, and HRMS. The kaempferol degradation pathway leading to the K1, K2, and K3 formation is proposed. It was observed that the more water concentration in the irradiation medium increases, the more K2 concentration increases. Comprehension of food preservation is not clear because many phenomena occurring during irradiation are not established. Radiolysis of kaempferol in water/methanol mixtures helps to elucidate the phenomenon and it is possible that during the treatment of nutriments by gamma-irradiation, a series of products such as depside K2 could be formed. Antioxidant properties of kaempferol radiolysis products were evaluated according to their capacity to decrease the EPR DPPH (1,1-diphenyl-2-picrylhydrazil) signal and to inhibit superoxide radicals formed by the enzyme reaction "xanthine + xanthine oxidase".  相似文献   

3.
Studies on bound (14)C-chlorsulfuron residues in soil   总被引：1，自引：0，他引：1  
The cause for phytotoxicity of bound residues of chlorsulfuron (2-chloro-N-[[4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino] carbonyl]benzenesulfonamide) to rotational crops is unknown. This study was conducted to determine the formation of nonextractable (bound) residues of chlorsulfuron in soil, and the distribution of bound residues in different organic matter fractions. The results showed that over 150 days, the extractable fraction of (14)C-residues decreased to 25.1% of applied chlorsulfuron, while bound residues concurrently increased to 47.1%. The distribution of (14)C-bound residues in soil organic matter fractions followed an order of humic acid (HA) < humin < fulvic acid (FA). Although the most bound residues were detected in the FA fraction, the amount associated with the humin fraction increased with time. After soil treatment by autoclaving, it was found that bound (14)C-chlorsulfuron residues became available again in the soil. One of the released products was 2-amino-4-hydroxyl-6-methyl-1,3,5-triazine (identified by GC-MS), which is a degradation product of chlorsulfuron.  相似文献   

4.
辐照对黄原胶分子量及抗氧化活性的影响   总被引：1，自引：0，他引：1  
李彦杰  哈益明  王锋  李咏富 《核农学报》2010,24(6):1208-1213
以0~500kGy 60Co γ射线对固态黄原胶进行辐照,研究辐照对黄原胶分子量及还原力、清除1,1-二苯基-2-苦基肼自由基（DPPH·）、超氧自由基（O2-·）及羟自由基（·OH）能力等抗氧化活性的影响。研究表明,10kGy的辐照可使黄原胶粘均分子量从1.71×106增加到2.23×106,超过10kGy后,黄原胶粘均分子量随辐照剂量的增大逐渐减少,500kGy时降为1.59×104。低于10kGy辐照,黄原胶的还原力、对DPPH·和对O2-·的清除率与剂量呈负相关,与对照相比,还原力降低了3.16%,对DPPH·和O2-·的清除率分别从17.37%和18.18%减少到16.87%和8.51%,增大辐照剂量,黄原胶的还原力和对DPPH·和O2-·的清除率与剂量呈正相关,500kGy时黄原胶的还原力比对照增加164.22%,对DPPH·和O2-·的清除率升高至60.79%和30.06%;对·OH清除能力与辐照剂量呈负相关,清除率从0kGy时的9.29%降低到500kGy时的3.63%。辐照可以引起黄原胶聚合或降解,从而导致其分子量及抗氧化活性发生显著变化。  相似文献   

5.
Residue analysis of the herbicide prometryn (2,4-bis(isopropylamino)-6-methylthio-1,3,5-triazine) is widely known, but an analytical method for determining its metabolities or degradation products in addition to the parent chemical has not yet been reported in the literature. The procedure reported here is for the extraction and determination of prometryn and 2 metabolites, 2-amino-4-isopropylamino-6-methyl-thio-1,3,5-triazine and 2,4-diamino-6-methylthio-1,3,5-triazine, in parsley. Crops were extracted with 2-propanol followed by concentration of the extract and partitioning with a minimum amount of hexane in the presence of a large excess of water to remove most of the green pigment. The aqueous phase was divided into 2 equal halves: (A) One-half portion was partitioned with dichloromethane in the presence of saturated sodium chloride solution, the dichloromethane phase was separated, and the aqueous phase was discarded. The organic solvent was evaporated, and the contents were reconstituted in petroleum ether before prometryn analysis. (B) The other half was made slightly alkaline with ammonium hydroxide solution and was partitioned with ethyl acetate in the presence of saturated sodium chloride solution. The ethyl acetate phase was concentrated, centrifuged to remove any turbidity, and analyzed for the 2 metabolities above. Fused silica capillary gas chromatography (GC) with nitrogen-phosphorus (N-P) detection was used for quantitation. The limit of detection was 0.05 mg/kg for all the compounds examined. Recoveries from fortified parsley samples ranged from 59 to 73% at fortification levels of 0.05 to 1.0 mg/kg.  相似文献   

6.
With the availability of an ultraweak chemiluminescence analyzer, it is possible to monitor the production of a specific oxygen-derived reactive species, such as hydroxyl radical ((*)OH), whenever a suitable chemiluminescent probe is obtainable. Reported herein is the development of a rapid and specific method for detecting (*)OH production using a specific probe, indoxyl-beta-glucuronide (IBG), a low-level chemiluminescence emitter. Using the Fenton reagent as a source of (*)OH, it was shown that IBG could elicit a very strong intensity of chemiluminescence (CL) (16200 +/- 200 photon counts/s). Conversely, IBG was shown to be insensitive to either superoxide radical or hydrogen peroxide with their CL intensities nearly close to the background values (25 +/- 5 and 180 +/- 20 photon counts/s, respectively). Furthermore, it was also shown that this IBG-based CL production could be effectively quenched by the addition of (*)OH scavengers such as sodium salicylate, dimethyl sulfoxide, and penicillamine to the assay system. Taken together, these data indicate that IBG is a specific CL probe suitable for monitoring the production of (*)OH. This system demonstrated inhibitory activities of various aqueous extracts of food constituents on the CL of hydroxyl radicals generated by Fenton's reagents with the order of scavenging efficiencies being Prunus mume > Cordyceps sinensin > Lilium lancifolium > Astragalus membranceus.  相似文献   

7.
Novel 2-(benzylamino)-4-methyl-6-(trifluoromethyl)-1,3,5-triazines have the same 1,3,5-triazine skeleton as atrazine, although some of them, for example, 2-(3-chlorobenzylamino)-4-methyl-6-(trifluoromethyl)-1,3,5-tria zin e [pI(50)(spinach) = 7.21], show a >3 times stronger photosynthetic electron transport inhibitory activity than atrazine [pI(50)(spinach) = 6.72]. The new triazines have only one amino group at the triazine ring, and their molecular shapes are different from atrazine. The replacement of the bound [(14)C]atrazine by 1,3,5-triazines was tested to determine whether the novel 1,3,5-triazine analogues exhibit the same binding pattern at the D1-protein as atrazine. It was found that [(14)C]atrazine bound to the D1-protein was replaced by the triazine tested by a clearly competitive interaction. Obviously, the novel 1,3,5-triazines are attached to the same binding niche as atrazine.  相似文献   

8.
Ellagic acid, a plant-derived polyphenol, inhibits gamma-radiation (hydroxyl radical) induced lipid peroxidation in rat liver microsomes in a dose- and concentration-dependent manner. Its antioxidant capacity has been estimated using the 1,1-diphenyl-2-picrylhydrazyl radical assay. To understand the actual mechanisms involved in antioxidant activity and the free radical scavenging ability,a nanosecond pulse radiolysis technique has been employed. The rate constants for the reactions of several reactive oxygen species and reactive nitrogen species such as hydroxyl, peroxyl, and nitrogen dioxide radicals have been found to be in the range of 10(6)-10(9) M(-1) s(-1). The ellagic acid radicals have been characterized by the absorption spectra and decay kinetics. Studies on the reactions of ellagic acid with the 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate) radical and the radicals of ellagic acid with ascorbate have been used to estimate its one-electron reduction potential. Ellagic acid has also been found to be a good scavenger of peroxynitrite. Using stopped-flow reaction analyzer with absorption detection, the rate constant for this reaction has been determined to be 3.7 x 10(3) M(-1) s (-1). The electron spin resonance spectra of the oxidized ellagic acid radicals have been recorded by horseradish peroxidase and hydrogen peroxide method.  相似文献   

9.
A set of equations in suggested to describe the kinetics of degradation of organic ompounds applied to soils ad the kinetics of growth of the inolved microorganisms:-dx/dt=jx kxm dm/dt=-fm gxm where x is the concentration of organic compound at time t,m is the numer of microorganisms capable of degrading the organic compound at time t,while j,k,f and g are positive constants,This model can satisfactorily be used to explain the degradation curve of organic compounds and the growth curve of the involved microorganisms.  相似文献   

10.
Anodic Fenton treatment (AFT) has been shown to be a promising technology in pesticide wastewater treatment. However, no research has been conducted on the AFT application to contaminated soils. In this study, the 2,4-D degradation kinetics of AFT in a silt loam soil slurry were investigated for the first time, and the effects of various experimental conditions including initial 2,4-D concentration, Fenton reagent delivery rate, amount of humic acid (HA) addition, and pH were examined. The 2,4-D degradation in soil slurry by AFT was found to follow a two-stage kinetic model. During the early stage of AFT (the first 4-5 min), the 2,4-D concentration profile followed a pseudo-first-order kinetic model. In the later stage (typically after 5 or 6 min), the AFT kinetic model provided a better fit. This result is most likely due to the existence of (*)OH scavengers and 2,4-D sorption on soil. The Fe(2+) delivery rate was shown to be a more significant factor in degradation rate than the H(2)O(2) delivery rate when the Fe(2+)/H(2)O(2) ratios were in the range of 1:2 to 1:10. The presence of HA in soil lowered the AFT rate, most probably due to the competition with 2,4-D for consumption of (*)OH and increased sorption of 2,4-D on soil. The optimal pH for 2,4-D degradation in soil slurry by AFT was observed to be in the range of pH 2-3.  相似文献   

11.
An analytical method is described for the extraction of metsulfuron-methyl from soil at sub-parts per billion levels (LOQ = 0.2 microgram kg(-1)). The herbicide was quantitatively determined and identified by ESI LC/MS/MS. The method has been applied to a field dissipation study in which metsulfuron-methyl was applied to spring barley at three dosage rates: 4, 8, and 16 g of active ingredient ha(-)(1). The results of 2 years are presented. The dissipation rate of metsulfuron-methyl in topsoil was very rapid, with a calculated half-life of 6.5 days. Laboratory mineralization studies with native soils in contrast to autoclaved soils indicated that microbial degradation of (14)C-labeled metsulfuron-methyl and (14)C-labeled 2-amino-4-methoxy-6-methyl-1,3,5-triazine in soil microcosms is an important factor for the complete degradation of metsulfuron-methyl in the field. However, the mineralization rate of the sulfonamide was much higher.  相似文献   

12.
The protective bioactivity of punicalagin, a high molecular weight polyphenol isolated from pomegranate fruit pith and carpellary membrane, against oxidative damages to lipids, amino acids constituting the proteins, and guanosine as a model for DNA has been investigated. The ABTS*-, guanosine, and tryptophan radical generated pulse radiolytically were repaired by punicalagin, k = (0.9-15) x 10(7) dm3 mol-1 s-1. The results are rationalized on the basis of the scavenging activity of punicalagin against various one-electron oxidizing radicals, namely, .OH, N3., and NO2. . The formation of the transient species in these reactions and the rate constants of the scavenging reactions have been probed using a time-resolved kinetic spectrophotometric technique. The antioxidant action of punicalagin is expressed not only through its scavenging reactions but also by its ability to form metal chelates. Binding of punicalagin with bovine serum albumin and metal ions such as iron and copper revealed different binding affinities, whereas its binding with DNA was very weak and nonspecific. In vitro cytotoxic studies against three cell lines, namely, Vero (normal African green monkey kidney cell line), Hep-2 (human larynx epithelial cancer cell line), and A-549 (human small cell lung carcinoma cell line) showed that this polyphenol is toxic only at higher concentration.  相似文献   

13.
This research is a continuation of a study on the behavior of hydrophobic organic compounds in the environment and describes the simultaneous abiotic degradation and sorption of pirimiphos-methyl (O-2-diethylamino-6-methylpyrimidin-4-yl O,O-dimethylphosphorothioate) under controlled conditions in soil/water slurries. A microfiltration-HPLC technique was employed to follow these processes in two well-characterized soils from the Middle Belt region of Nigeria. Rapid sorption of the pesticide occurs during the first 10 min of equilibration and accounted for 37% of the original pirimiphos-methyl in the Rhodic Kandiustalf soil and for 41% of the original concentration in Aquic Ustropept soil. Subsequent slow processes were followed during the remaining 30 days of the experiment. During this time, first-order rate constants for disappearance from solution of pirimiphos-methyl were found to have values of 6.1 x 10(-)(7) and 9.8 x 10(-)(7) s(-)(1) for the Rhodic and Aquic soils, respectively. Similarly, rate constants for production of the product, pyrimidinol, were calculated to be 6.0 x 10(-)(7) and 9.4 x 10(-)(7) s(-)(1) for the Rhodic and Aquic soils, respectively, giving pesticide degradation half-lives of 13 and 8.5 days. Disappearance of the pesticide is discussed in terms of a scheme involving both sorptive uptake by the soil and degradation by hydrolysis in the presence of the soil matrix. The labile sorption capacities for pirimiphos-methyl in the Rhodic and Aquic soils were found to be 0.75 and 0.90 micromol g(-)(1), respectively.  相似文献   

14.
The essential oils of Ocimum basilicum L., Origanum vulgare L., and Thymus vulgaris L. were analyzed by means of gas chromatography-mass spectrometry and assayed for their antioxidant and antimicrobial activities. The antioxidant activity was evaluated as a free radical scavenging capacity (RSC), together with effects on lipid peroxidation (LP). RSC was assessed measuring the scavenging activity of the essential oils on 2,2-diphenyl-1-picrylhydrazil (DPPH(*)) and OH(*) radicals. Effects on LP were evaluated following the activities of essential oils in Fe(2+)/ascorbate and Fe(2+)/H(2)O(2) systems of induction. Essential oils exhibited very strong RSCs, reducing the DPPH radical formation (IC(50)) in the range from 0.17 (oregano) to 0.39 microg/mL (basil). The essential oil of T. vulgaris exhibited the highest OH radical scavenging activity, although none of the examined essential oils reached 50% of neutralization (IC(50)). All of the tested essential oils strongly inhibited LP, induced either by Fe(2+)/ascorbate or by Fe(2+)/H(2)O(2). The antimicrobial activity was tested against 13 bacterial strains and six fungi. The most effective antibacterial activity was expressed by the essential oil of oregano, even on multiresistant strains of Pseudomonas aeruginosa and Escherichia coli. A significant rate of antifungal activity of all of the examined essential oils was also exhibited.  相似文献   

15.
Atrazine and metolachlor degradation in subsoils   总被引：6，自引：0，他引：6  
Degradation of atrazine [2-chloro-4-etylamino-6-isopropylamino-1,3,5-triazine] and metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)-acetamide] in sterile and non-sterile soil samples collected at two different soil depths (0-20 and 80-110 cm) and incubated under aerobic and anaerobic conditions was studied. Under aerobic conditions, the half-life of atrazine in non-sterile surface soil was 49 days. In non-sterile subsoil, the half-life of atrazine (119 days) was increased by 2.5 times compared in surface soils and was not statistically different from half-lives in sterile soils (115 and 110 days in surface soil and subsoil, respectively). Metolachlor degradation occurred only in non-sterile surface soil, with a half-life of 37 days. Under anaerobic conditions, atrazine degradation was markedly slower than under aerobic conditions, with a half-life of 124 and 407 days in non-sterile surface soil and non-sterile subsoil, respectively. No significant difference was found in atrazine degradation in both sterile surface soil (693 days) and subsoil (770 days). Under anaerobic conditions, degradation of metolachlor was observed only in non-sterile surface soil. Results suggest that atrazine degraded both chemically and biologically, while metolachlor degraded only biologically. In addition, observed Eh values of soil samples incubated under anaerobic conditions suggest a significant involvement of soil microorganisms in the overall degradation process of atrazine under anaerobic conditions.  相似文献   

16.
本文以0、2、4、6kGy剂量60Co γ射线辐照发酵香肠,以水分活度、水分含量、pH值、含盐量、氨基酸总量、非蛋白氮、总氮、硫代巴比妥酸值、挥发性风味物质、肌浆蛋白与肌原纤维蛋白降解情况为指标,研究辐照对香肠品质的影响。结果表明：发酵香肠经不同剂量辐照后水分含量差异显著(P<0.05),氯化钠含量差异并不显著,而0、2kGy辐照后发酵香肠的pH值显著高于4、6kGy辐照,4kGy剂量辐照的发酵香肠中氨基酸总量显著高于2、6kGy处理的样品(P<0.05),4kGy剂量辐照香肠烯烃、酸和酮类物质含量最多,6kGy辐照组中醇类物质含量最多。辐照处理的发酵香肠中肌浆蛋白和肌原蛋白的降解情况低于对照。  相似文献   

17.
The antioxidant ability of the flavanol catechin and its planar derivative, catechin 1 (PC1), was explored using the DF/B3LYP theoretical approach. Their potentiality in the hydrogen abstraction and electron transfer reactions, the main working mechanisms of antioxidants, was evaluated by computing the values of two key parameters, which are the OH bond dissociation energy and the ionization potential. Results indicated that the effect of a planar arrangement in the catechin molecule is small in the case of the hydrogen abstraction but greater for the electron transfer, since the in vacuo ionization potential value decreases by about 3 kcal/mol. The reaction of these molecules with the hydroperoxyl radical (*)OOH indicated that the H(*) abstraction is faster with the planar catechin.  相似文献   

18.
Recently, phytochemical compounds present in legumes have gained a lot of interest because they are considered to be possible chemopreventive agents. In the present study, 14 polyphenolic compounds were extracted and identified from two unique varieties of Leguminosae family plants cultivated in Greece and screened for their antioxidant and chemopreventive properties. Ten polyphenolic fractions, which are mainly mixtures of two compounds and five pure flavonoids, were isolated from the methanolic extracts of aerial plant parts of Vicia faba and Lotus edulis (Leguminosae), respectively. All of these fractions exhibited significant DPPH(*) radical scavenging capacity. Furthermore, they exerted significant protective activity against free radical-induced DNA damage. This activity was more potent against ROO(*) radical-induced DNA damage than against that induced by OH(*) radicals. Finally, they exhibited significant ability to inhibit the activity of the topoisomerase I enzyme. These results imply that the polyphenolic compounds identified in the fractions were responsible of the observed properties of the fractions and the initial extracts and indicate different mechanisms by which these phenolic compounds may act as chemopreventive agents.  相似文献   

19.
The B-ring substitution pattern of flavonols is a significant structural feature for their function as free radical scavengers and antioxidants. In this paper, four differently substituted B-ring hydroxylation flavonols (galangin, kaempferol, quercetin, and myricetin) and a flavonol glycoside (quercitrin) were studied for their ability to bind BSA by quenching the protein intrinsic fluorescence. From the spectra obtained, the biomolecular quenching constants, the apparent static binding constants, and the binding site values were calculated. The B-ring hydroxylation of flavonols significantly affected the binding/quenching process; in general, the binding affinity increased with the number of hydroxyl groups on the B-ring. The binding constants ( Ka) were determined as myricetin (4.90 x 10(8) L/mol) > quercetin (3.65 x 10(7) L/mol) > kaempferol (2.57 x 10(6) L/mol) > galangin (6.43 x 10(5) L/mol). The glycoside substitute at the C-ring position decreased the binding affinity. The chromatographic retention factor ( K') and logarithms of apparent partition coefficient (log Kow) were linear to the logarithms of apparent binding constants (log Ka) for flavonols with increasing hydroxyl groups on the B-ring. These results showed that the hydrogen bond force play an important role in binding flavonols to BSA. These results are also in agreement with the generally accepted structure-dependent free radical scavenger and antioxidant abilities of flavonols.  相似文献   

20.
The herbicide atrazine [2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine] was applied to corn at recommended rates over a period of 18 years until 1988. The investigated field was sampled down to a depth of 10 m in 1989 and 1991. In both years residues of atrazine were determined down to 10 m depth by HPLC-analysis of soil extracts in concentrations of up to 12 μg/kg. Batch-experiments were conducted to establish sorption isotherms of various soil layers. Numerical simulations of the migration of atrazine, based on the Richards-equation and the convection-dispersion-equation with first-order degradation were performed and compared to the measurements. Depth-dependent distribution of atrazine residues could be roughly reproduced by calculations, but the calculated depth-profiles of atrazine concentrations varied strongly within the variability of the sensitive parameters. The deterministic model used was therefore not able to predict the amount of pesticide residues in groundwater recharge precisely.  相似文献   

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