Pesticide activation reactions

Several 3-aryl-2-methylimidazo[4,5-b]pyridines (36 X = H, R = H, 4-F, 4-Et X = Cl, R = H, 4-F, 3-CF3, 2,4-Me2, 2,4-Ch, 2-Me-6-Et, 3-CF3-4-C1) with pesticidal activity have been prepared in moderate yields by the reaction of /V-(2-chloro-3-pyridyl)acetamides (37) with aromatic amines in the presence of P2O5 and Et3N-HCl at 150 C.140 With X = H the cyclized products were isolated directly, whereas with X = Cl treatment of the intermediate amidines (38) with K2CO3 in DMF was required to arrive at the final cyclized product. 

Inhibitors of a herbivore s ability to detoxify plant toxicants may expectedly be more slow-acting than neurotoxicants such as organophosphates. Nevertheless, securance of synergists of dietary toxicants that complement activation reactions and inhibit detoxification reactions in the targeted pests will have potential for IPM, since they should be compatible or moreover, augment plant antibiosis, natural enemies and concurrently used pesticides. 

For many eplgnetlc carcinogens, such as hormones and or-ganochlorlne pesticides, metabolism leads to detoxified products. However, an activation reaction metabolizes certain Immunosuppressants to their cytotoxic forms. It has been suggested that Induction of a P-452 oxidation of fatty acids may underlie the ability of agents to Induce peroxisomes (4). The latter event. Is believed to underlie the carcinogenicity of peroxisome proliferators (5), among which are some pesticides (6). 

A dramatic increase in the number of papers on the synthesis of derivatives of thiophensulphonic acids can be noted, and is certainly connected with the interest in such compounds with herbicidal, bacteriocidal or pesticidal activity. The reaction kinetics of substi-... 

Detoxification and Activation Reactions From an acute toxicity standpoint, the metabolism of pesticides by most organisms usually results in their conversion to products of lesser biological activity. There are several reasons v y such would be expected, not the least of which is the fact that the detoxification systems of living organisms have evolved for just such a purpose. Certainly, too, structure-activity relationships are usually so critical that toxicity, especially in the acute sense, is often greatly reduced or totally eliminated as the result of essentially any chemical transformation. Numerous examples of metabolic reactions leading to more-or-less complete pesticide detoxification could be cited, but the o-deethylation of chlorfenvinphos and the ester hydrolysis of carbaryl, both insecticides, are shown as somewhat representative examples (Figure 7). 

Toxin (Enzyme Inhibition) Biosensors Enzyme affectors (inhibitors and activators) that influence the rate of biocatalytic reactions can also be measured. Sensing probes for organophosphate and carbamate pesticides, for the respiratory... 

Your children may be exposed to endosulfan if unquahfied people apply pesticides around your home. In some cases, the use of pesticides that have been banned for use in homes has turned homes into hazardous waste sites. Your state licenses each person qualified to apply pesticides using EPA standards and further certifies each person qualified to apply restricted use pesticides. Ask to see the license and certification of anyone who applies pesticides for you. Also ask for the brand name of the pesticide, a material safety data sheet (MSDS), the name of the product s active ingredient, and the EPA registration number. Ask whether EPA has designated the pesticide for restricted use and what the approved uses are. This information is important if you or your family have a reaction to the product. 

Phosphorus-containing pesticides la 254 Phosphorus insecticides lb 83 Phosphorus pesticides lb 32 Photochemical activation lb 13 Photochemical reactions lb 15,17 Photodiodes la 24,29 Photo effect, external la 24 -, internal la 24, 29 Photo element la 24,29 Photography, exposure times la 137 -, instmmentation la 137 Photomultiplier la 25ff -, disadvantages la 27 -, energy distribution la 26 -, head on la 27 -, maximum sensitivity la 28 -, side on la 27 -, spectral sensitivity la 28 -, window material la 28 Photocells la 25 Phloxime lb 116... 

Other interesting examples of proteases that exhibit promiscuous behavior are proline dipeptidase from Alteromonas sp. JD6.5, whose original activity is to cleave a dipeptide bond with a prolyl residue at the carboxy terminus [121, 122] and aminopeptidase P (AMPP) from E. coli, which is a prohne-specific peptidase that catalyzes the hydrolysis of N-terminal peptide bonds containing a proline residue [123, 124]. Both enzymes exhibit phosphotriesterase activity. This means that they are capable of catalyzing the reaction that does not exist in nature. It is of particular importance, since they can hydrolyze unnatural substrates - triesters of phosphoric acid and diesters of phosphonic acids - such as organophosphorus pesticides or organophosphoms warfare agents (Scheme 5.25) [125]. 

Attempts have been made to apply the structure-activity concept (Hansch and Leo 1995) to environmental problems, and this has been successfully applied to the rates of hydrolysis of carbamate pesticides (Wolfe et al. 1978), and of esters of chlorinated carboxylic acids (Paris et al. 1984). This has been extended to correlating rates of biotransformation with the structure of the substrates and has been illustrated with a number of single-stage reactions. Clearly, this approach can be refined with the increased understanding of the structure and function of the relevant degradative enzymes. Some examples illustrate the application of this procedure ... 

Chohnesterase-inhibiting pesticides (e g., organophosphate and carbamate pesticides) are detected by dipping the developed chromatogram in a solution of the enzyme chohnesterase followed by incubation for a short period. Then the plate is dipped in a substrate solution, e.g., 1-naphthyl acetate/fast blue salt B. In the presence of the active enzyme, 1-naphthyl acetate is hydrolyzed to 1-naphthol and acetic acid, and the 1-naphthol is coupled with fast blue salt B to form a violet-blue azo dye. The enzyme is inhibited by the pesticide zones, so the enzyme-substrate reaction does not occur pesticides are, therefore, detected as colorless zones on a violet-blue background [36]. 

Because process mixtures are complex, specialized detectors may substitute for separation efficiency. One specialized detector is the array amperometric detector, which allows selective detection of electrochemically active compounds.23 Electrochemical array detectors are discussed in greater detail in Chapter 5. Many pharmaceutical compounds are chiral, so a detector capable of determining optical purity would be extremely useful in monitoring synthetic reactions. A double-beam circular dichroism detector using a laser as the source was used for the selective detection of chiral cobalt compounds.24 The double-beam, single-source construction reduces the limitations of flicker noise. Chemiluminescence of an ozonized mixture was used as the principle for a sulfur-selective detector used to analyze pesticides, proteins, and blood thiols from rat plasma.25 Chemiluminescence using bis (2,4, 6-trichlorophenyl) oxalate was used for the selective detection of catalytically reduced nitrated polycyclic aromatic hydrocarbons from diesel exhaust.26... 

Cholinesterase Activity as a Biosensor Reaction for Natural Allelochemicals Pesticides and Pharmaceuticals... 

Procedure Allelochemical and a compound belonging to natural artificial pesticides and medicinal drugs is preliminary added into the reaction media (see section Add). The difference in cholinesterase activity (measured as shown in sections 15.3) between a control (without the substance added) and the experimental variant is estimated. The results are compared with the effects of the cholinesterase inhibitors neostigmine and physostigmine. 

In AChE-based biosensors acetylthiocholine is commonly used as a substrate. The thiocholine produced during the catalytic reaction can be monitored using spectromet-ric, amperometric [44] (Fig. 2.2) or potentiometric methods. The enzyme activity is indirectly proportional to the pesticide concentration. La Rosa et al. [45] used 4-ami-nophenyl acetate as the enzyme substrate for a cholinesterase sensor for pesticide determination. This system allowed the determination of esterase activities via oxidation of the enzymatic product 4-aminophenol rather than the typical thiocholine. Sulfonylureas are reversible inhibitors of acetolactate synthase (ALS). By taking advantage of this inhibition mechanism ALS has been entrapped in photo cured polymer of polyvinyl alcohol bearing styrylpyridinium groups (PVA-SbQ) to prepare an amperometric biosensor for... 

Although the inhibition-based biosensors are sensitive, they are poor in selectivity and are rather slow and tedious since the analysis involves multiple steps of reaction such as measuring initial enzyme activity, incubation with inhibitor, measurement of residual activity, and regeneration and washing. Biosensors based on direct pesticide hydrolysis are more straightforward. The OPH hydrolyzes ester in a number of organophospho-rus pesticides (OPPs) and insecticides (e.g. paraoxon, parathion, coumaphos, diazinon) and chemical warfare agents (e.g. sarin) [53], For example, OP parathion hydrolyzes by the OPH to form p-nitrophenol, which can be measured by anodic oxidation. Rainina... 

It is now clear that the fate of chemicals in the environment is controlled by a combination of three groups of factors. First are the prevailing environmental conditions such as temperatures, flows and accumulations of air, water and solid matter and the composition of these media. Second are the properties of the chemicals which influence partitioning and reaction tendencies, i.e., the extent to which the chemical evaporates or associates with sediments, and how fast the chemical is eventually destroyed by conversion to other chemical species. Third are the patterns of use, into which compartments the substance is introduced, whether introduction is episodic or continuous and in the case of pesticides how and with which additives the active ingredient is applied. 

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