Biomimetic oxidation of plant protecting agents

The suitability of two in vitro oxidation systems as chemical models for the biological degradation of plant protecting agents has been investigated. As representative herbicides diclofop, fenoxaprop, isoproturon, linuron and monolinuron have been oxidised by two systems, the Fentons reagent and the ascorbic acid oxidation system (AAOS) and the results compared to those of the known metabolic pathways of these compounds. The herbicides have been oxidised by Fentons reagent (hydroxy radicals). The main products were isolated by preparative scale HPLC and identified with ¹H-NMR and MS. Some of the products have been identified by comparing their retention times and UV/Vis-spectra to those of standard compounds. Several products known from biological degradation are also found after chemical oxidation, however, notable differences between the two pathways have been observed, for instance in the case of diclofop. Oxidation by the AAOS leads to comparable results. Reaction rates for the oxidation with the AAOS have been studied and compared with data known from degradation studies of the herbicides in soil. Compounds which are slowly degraded in soil are oxidised more slowly in the biomimetic process than those with a fast degradation in soil.     

Determination of sulfonylurea degradation products in soil by liquid chromatography-ultraviolet detection followed by confirmatory liquid chromatography-tandem mass spectrometry.

A method based on liquid extraction followed by sample enrichment on reversed-phase solid-phase extraction was developed for the extraction of five degradation products of four sulfonylurea herbicides (chlorsulfuron, metsulfuron-methyl, thifensulfuron-methyl and tribenuron-methyl) from soil. The compounds have been quantified by LC-UV and identified by tandem LC-MS with electrospray ionization or atmospheric pressure chemical ionization. The limits of detection for the five compounds were between 10 and 50 micrograms kg-1. The method has been applied to the extraction of soil samples after microbial degradation of sulfonylurea herbicides.     

The structure and stability of oxidised polybutadiene

Polybutadiene has been oxidised at 0–20°C for periods from one day up to several months and also at elevated temperatures. Microstructural changes in the polymer due to oxidation have been followed by ir and uv spectroscopy. Oxidised samples of the polymer have been degraded in nitrogen or in vacuum under programmed heating conditions by TG, DSC and thermal volatilisation analysis (TVA). In TVA degradations, non-condensable gaseous products have been studied by adsorption TVA, condensable volatile products have been separated by subambient TVA for identification, cold ring fraction materials have been examined spectroscopically and the ir spectrum of the polymer residue, after degradation to 440°C, has also been obtained. From this considerable amount of data it has been possible to propose structures present in oxidised polybutadienes and to suggest some degradative processes involved in the subsequent thermal degradation. Oxidation leads to a considerable lowering of the threshold temperature for the main decomposition process; in samples oxidised at low temperatures, an additional early stage of degradation, commencing near 100°C, is found, due to peroxide decomposition.     

Thio-organotin Antioxidants for Polypropylene: Reactivity towards t-Butyl Hydroperoxide

Various thio-organotin compounds have been reacted with t-butyl hydroperoxide in order to determine whether this oxidation can be responsible for the stabilizing capacity of some thio-organotins towards polyolefin degradation. The kinetics of t-butyl hydroperoxide disappearance, in the presence of thiotin compounds, shows different reactivity according to the structure of oranometallic reagent. Product analysis indicates organotin oxide, dialkyl disulfide and t-butanol as major reaction products. The reactivity sequence towards hydroperoxide is the same as the order observed for polypropylene stabilization.     

Synthesis,Herbicidal Activity,Crop Safety and Soil Degradation of Pyrimidine- and Triazine-Substituted Chlorsulfuron Derivatives

Chlrosulfuron, a classical sulfonylurea herbicide that exhibits good safety for wheat but causes a certain degree of damage to subsequent corn in a wheat–corn rotation mode, has been suspended field application in China since 2014. Our previous study found that diethylamino-substituted chlorsulfuron derivatives accelerated the degradation rate in soil. In order to obtain sulfonylurea herbicides with good crop safety for both wheat and corn, while maintaining high herbicidal activities, a series of pyrimidine- and triazine-based diethylamino-substituted chlorsulfuron derivatives (W102–W111) were systematically evaluated. The structures of the synthesized compounds were confirmed with ¹H NMR, ¹³C NMR, and HRMS. The preliminary biological assay results indicate that the 4,6-disubstituted pyrimidine and triazine derivatives could maintain high herbicidal activity. It was found that the synthesized compounds could accelerate degradation rates, both in acidic and alkaline soil. Especially, in alkaline soil, the degradation rate of the target compounds accelerated more than 22-fold compared to chlorsulfuron. Moreover, most chlorsulfuron analogs exhibited good crop safety for both wheat and corn at high dosages. This study provided a reference for the further design of new sulfonylurea herbicides with high herbicidal activity, fast degradation rates, and high crop safety.     

3种芳氧苯氧丙酸类除草剂在CDMPC与万古霉素手性固定相上的对映体分离

在纤维素三（3,5-二甲基苯基氨基甲酸酯）（CDMPC）手性柱上成功分离了3种高效芳氧苯氧丙酸类除草剂——稳杀得、千金和禾草灵。正相系统下,分别考察了流动相醇类添加剂的种类、浓度以及溶质结构对手性分离的影响,3种溶质中千金的保留最强而禾草灵的分离效果最好。并在万古霉素手性固定相上对3种芳氧苯氧丙酸类除草剂进行了手性拆分。在正相流动相中,它们在万古霉素手性固定相上的手性分离效果明显不如在CDMPC上的好。探讨了2种手性固定相对3种溶质的手性识别机理。     

The Use of Various Chromatographic Techniques for the Determination of Phenylurea Herbicides and Their Corresponding Anilines in Environmental Samples,II. Applications

Abstract

In earlier work, various strategies have been developed for the trace-level determination of phenylurea herbicides and the anilines which are their main degradation products. They include catalytic hydrolysis of the phenylureas on silica, liquid chromatographic fractionation of complex mixtures of herbicides and anilines, derivatization of anilines and herbicides with electron-capture-sensitive reagents, and final analysis by means of capillary gas chromatography. In the present paper, the application of these principles to trace-level analysis of surface water, soil and crop samples is demonstrated.     

Total degradation of fenitrothion and other organophosphorus pesticides by catalytic oxidation employing Fe-TAML peroxide activators

A Fe-TAML/H2O2 catalytic oxidation process achieves facile in-solution total degradation of fenitrothion and two other organophosphorus (OP) pesticides. Degradation products have been identified and quantified providing evidence for oxidative hydrolysis, oxidative desulfuration, perhydrolysis, and deep oxidation. Degradation pathways can be selected by pH control to completely obviate all toxic residuals. Aquatic toxicity assays support the environmental compatibility of the degradation process.     

Analysis of the degradation products of diproteverine by moving belt LC/MS

Moving belt LC/MS has been used to identify the degradation products of the slow calcium membrane channel inhibitor, Diproteverine, after storage at elevated temperature and humidity. The major products observed result from oxidation. Two of these products, both ketones, yield [M ? 14 + H]⁺ ions by chemical ionization. These unusual ions also occur for some simple aromatic ketones used as model compounds and are shown to arise by reduction of the carbonyl group to a methylene by the reagent gas.     

Studies of the soluble part of oxidised coals

Soluble products obtained from the oxidation of four types of coal, each characterised by different degree of coalification and different degree of sulphur content, are studied. The coals are oxidised with peracetic acid (PAA) and nitric acid. Analyses are performed by Atmospheric Pressure-Temperature Programmed Reduction (AP-TPR) and Fourier Transform Infrared Spectroscopy (FTIR). The soluble products contain much more sulphur than the insoluble products of oxidation. The products obtained from the reaction with HNO₃ contain higher amounts of inorganic sulphur compounds, while those obtained from the reaction with PAA are characterised by an increased content of organic sulphur species.     

Alkaline Soil Degradation and Crop Safety of 5-Substituted Chlorsulfuron Derivatives

Sulfonylurea herbicides can lead to serious weed resistance due to their long degradation times and large-scale applications. This is especially true for chlorsulfuron, a widely used acetolactate synthase inhibitor used around the world. Its persistence in soil often affects the growth of crop seedlings in the following crop rotation, and leads to serious environmental pollution all over the world. Our research goal is to obtain chlorsulfuron-derived herbicides with high herbicidal activities, fast degradation times, as well as good crop safety. On account of the slow natural degradation of chlorsulfuron in alkaline soil, based on the previously reported results in acidic soil, the degradation behaviours of 5-substituted chlorsulfuron analogues (L101–L107) were investigated in a soil with pH 8.39. The experimental data indicated that 5-substituted chlorsulfuron compounds could accelerate degradation rates in alkaline soil, and thus, highlighted the potential for rational controllable degradation in soil. The degradation rates of these chlorsulfuron derivatives were accelerated by 1.84–77.22-fold, compared to chlorsulfuron, and exhibited excellent crop safety in wheat and corn (through pre-emergence treatment). In combination with bioassay activities, acidic and alkaline soil degradation, and crop safety, it was concluded that compounds L104 and L107, with ethyl or methyl groups, are potential green sulfonylurea herbicides for pre-emergence treatment on wheat and corn. This paper provides a reference for the further design of new sulfonylurea herbicides with high herbicidal activity, fast, controllable degradation rates, and high crop safety.     

Experimental assessment of electrochemical processes in the remediation of atrazine contaminated soils

The electrochemical oxidation of an atrazine solution obtained from a flushing treatment of a contaminated soil was investigated. The influence of ethanol on atrazine oxidation was studied. Results show that the electrogenerated Fenton's reagent provides a complete degradation of atrazine and its main chlorinated by-products via N-dehalkylation and dechlorination. This process therefore presents an effective alternative to the chemical oxidation treatment which necessarily needs a further biological state.     

The Formation of Methyl Ketones during Lipid Oxidation at Elevated Temperatures

Lipid oxidation and the resulting volatile organic compounds are the main reasons for a loss of food quality. In addition to typical compounds, such as alkanes, aldehydes and alcohols, methyl ketones like heptan-2-one, are repeatedly described as aroma-active substances in various foods. However, it is not yet clear from which precursors methyl ketones are formed and what influence amino compounds have on the formation mechanism. In this study, the formation of methyl ketones in selected food-relevant fats and oils, as well as in model systems with linoleic acid or pure secondary degradation products (alka-2,4-dienals, alken-2-als, hexanal, and 2-butyloct-2-enal), has been investigated. Elevated temperatures were chosen for simulating processing conditions such as baking, frying, or deep-frying. Up to seven methyl ketones in milk fat, vegetable oils, and selected model systems have been determined using static headspace gas chromatography-mass spectrometry (GC-MS). This study showed that methyl ketones are tertiary lipid oxidation products, as they are derived from secondary degradation products such as deca-2,4-dienal and oct-2-enal. The study further showed that the position of the double bond in the precursor compound determines the chain length of the methyl ketone and that amino compounds promote the formation of methyl ketones to a different degree. These compounds influence the profile of the products formed. As food naturally contains lipids as well as amino compounds, the proposed pathways are relevant for the formation of aroma-active methyl ketones in food.     

Ion trap tandem mass spectrometry study of dexamethasone transformation products on light activated TiO2 surface

The photocatalytic transformation of dexamethasone and the formation of its intermediate compounds have been studied using titanium dioxide as a photocatalyst. The degradation of dexamethasone occurs easily through the formation of several hydroxy derivatives whose characterization has been made by HPLC/MS/MS. Even if both oxidative and reductive processes can be operating, only oxidative products have been identified in air saturated aqueous suspensions. A pattern of reaction pathways accounting for the observed intermediates is proposed. The obtained experimental evidence may be rationalized postulating the existence of a double initial mechanism. A single oxidation step resulting from the attack by one ·OH radical leading to the formation of five hydroxy-derivatives and a concomitant attack involving two ·OH radicals leading to the hydroxylation of the quinoid moiety of the molecule.     

Stability study on a Westöö-based methodology to determine organomercury compounds in polluted soil samples

This paper concerns with the evaluation of a speciation methodology for organomercury compounds in soil samples. The methodology used is based on the Westöö method, which includes an acid leaching of the soil followed by an organic solvent extraction and a re-extraction with a selective aqueous reagent (cysteine). The separation and quantification of organomercury compounds is achieved by capillary electrophoresis technique, using an ultraviolet-visible detection system (HPCE-UV). The main steps in the speciation process are discussed, from the point of view of possible degradation processes. Frozen, de-frozen and non-frozen soil samples have been analyzed, characterizing the influence of light and temperature. Equally, the effect of light and temperature, as well as the chemical form of cysteine, have been analyzed on aqueous extracts. Organomercury degradation has been observed in the aqueous phase and related results are discussed.     

Studies on the behaviour of dihalogenated hydroxybenzonitriles in water

The degradation behaviour of the pesticides bromofenoxim, bromoxynil, bromoxynil octanoate, ioxynil, chloroxynil and mecoprop has been studied in natural aerobic water. UV spectra of the herbicides dissolved in bidistilled or surface water have been recorded under different pH and irradiation conditions as a function of time. The compounds can be divided into two groups; the first group — bromoxynil, ioxynil, chloroxynil, mecoprop — is stable for several weeks, while the compounds of the second group — bromofenoxim and bromoxynil octanoate — start to decompose immediately. The rate of decomposition depends mainly on the irradiation or on the biological activity of the surface water. Therefore, much greater stabilities can be expected during underground passage. This instability must be considered during the determination of these herbicides.Dedicated to Professor Dr. Dieter Klockow on the occasion of his 60th birthday     

Designing an enzyme-based nanobiosensor using molecular modeling techniques

Nanobiosensors can be built via functionalization of atomic force microscopy (AFM) tips with biomolecules capable of interacting with the analyte on a substrate, and the detection being performed by measuring the force between the immobilized biomolecule and the analyte. The optimization of such sensors may require multiple experiments to determine suitable experimental conditions for the immobilization and detection. In this study we employ molecular modeling techniques to assist in the design of nanobiosensors to detect herbicides. As a proof of principle, the properties of acetyl co-enzyme A carboxylase (ACC) were obtained with molecular dynamics simulations, from which the dimeric form in an aqueous solution was found to be more suitable for immobilization owing to a smaller structural fluctuation than the monomeric form. Upon solving the nonlinear Poisson-Boltzmann equation using a finite-difference procedure, we found that the active sites of ACC exhibited a positive surface potential while the remainder of the ACC surface was negatively charged. Therefore, optimized biosensors should be prepared with electrostatic adsorption of ACC onto an AFM tip functionalized with positively charged groups, leaving the active sites exposed to the analyte. The preferential orientation for the herbicides diclofop and atrazine with the ACC active site was determined by molecular docking calculations which displayed an inhibition coefficient of 0.168 μM for diclofop, and 44.11 μM for atrazine. This binding selectivity for the herbicide family of diclofop was confirmed by semiempirical PM6 quantum chemical calculations which revealed that ACC interacts more strongly with the herbicide diclofop than with atrazine, showing binding energies of -119.04 and +8.40 kcal mol(-1), respectively. The initial measurements of the proposed nanobiosensor validated the theoretical calculations and displayed high selectivity for the family of the diclofop herbicides.     

The Reaction of Japanese Reagent with Aminoacetamide with Alkyl Group

2,4-Bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide¹,commonly known as Lawesson's reagent (LR,1a),and Japanese Reagent (1b),are not only thiating agent for diverse carbonyl compounds^1-3, but also they undergoes ring-closure reactions with contain substrates containing two functional groups to give phosphorus heterocycles which contain phosphonothioyliene {C₆H₄-P(S)〈} moiety. These heterocyclic compounds are of potential interest as herbicides,insecticides,and fungicides^4,5. Glycinamides are known as biologically active materials, for example, herbicides, plant-growth regulator⁶. In order to look for potent herbicides⁷ and to extent the use of Japanese Reagent to other bifunctional substrates,its reactions with 3-alkyl-glycinamides 2 have been investigated and found to give new phosphorus heterocycles which possess Significant selective herbicidal activity against rape. Here are our results.     

Controllable Effect of Structural Modification of Sulfonylurea Herbicides on Soil Degradation

The study of soil degradation behaviors of sulfonylurea herbicides in relation to their different structural attributes is utmost important for us to comprehend the development of new eco‐friendly herbicides. It is postulated that the structural modification of the chemical structures could influence their degradation rates in soil. Nine devised structures were synthesized to study their herbicidal activity as well as their soil degradation behaviors respectively. The novel compounds I‐3 – I‐7 were characterized by UV, ¹H NMR and ¹³C NMR, MS and EA. Bioassays indicated that most of target compounds displayed superior herbicidal activities in comparison with Chlorsulfuron. Soil degradation results further confirmed our previous assumption that the introduction of electron‐donating substituents at 5^th position of the benzene ring distinctly increased their degradation rates, among which dimethylamino and diethylamino groups can adjust the degradation rate to a more favorable status.