Monooxygenases reactions effected

Monooxygenases, 25 382, 383 reactions effected by, 25 383 Mono-oxygen species, characterization, 32 111-112... 

Miller, S.M. and Khnman, J.P. (1985). Secondary isotope effects and structure-reactivity correlations in the dopamine heta-monooxygenase reaction evidence for a chemical mechanism. Biochemistry 24, 2114-2127... 

Noncompetitive inhibitors can bind to both the enzyme and enzyme-substrate complex to form either an enzyme-inhibitor complex or an enzyme-inhibitor-substrate complex. The net result is a decrease in Vmax but no change in Km. Metyrapone (Figure 9.6), a well-known inhibitor of monooxygenase reactions, can also, under some circumstances, stimulate metabolism in vitro. In either case the effect is noncompetitive, in that the Km does not change, whereas Vm. does, decreasing in the case of inhibition and increasing in the case of stimulation. 

The catalyst indicated extremely high resistance to the effects of oxidants and their intermediates and relatively high temperature, e.g. it preserves the ability to epoxidize during the whole time of the biomimic tests. Owing to the mentioned properties of the mimic, kinetic regularities of current monooxygenase reaction were studied in a broad range of reaction parameters with reproducible results. 

Tian GC, Berry JA, Klinman JP. 1994. 0-18 kinetic isotope effects in the dopamine P-monooxygenase reaction evidence for a new chemical mechanism in nonheme metal-lomonooxygenases. Biochemistry 33 226—234. 

One-step hydroxylation of aromatic nucleus with nitrous oxide (N2O) is among recently discovered organic reactions. A high eflSciency of FeZSM-5 zeolites in this reaction relates to a pronounced biomimetic-type activity of iron complexes stabilized in ZSM-5 matrix. N2O decomposition on these complexes produces particular atomic oj gen form (a-oxygen), whose chemistry is similar to that performed by the active oxygen of enzyme monooxygenases. Room temperature oxidation reactions of a-oxygen as well as the data on the kinetic isotope effect and Moessbauer spectroscopy show FeZSM-5 zeolite to be a successfiil biomimetic model. 

Phenol is catabolized by liver microsomal monooxygenases to hydroxylated products (e.g., 1,4-dihydroxybenzene) that can undergo further conversion to a variety of electrophilic substances (e.g., benzoquinones). Such reactions may be involved in generating reactive toxic intermediates in the liver (Eastmond et al. 1986 Lunte and Kissinger 1983 Subrahmanyam and O Brien 1985). Based on the available data, hepatic effects are unlikely to occur at the exposure levels found in the environment or near hazardous waste sites. 

Natural (-)-cocaine (7.57, Fig. 7.8), which has the (2/ ,3S)-configuration, is a relatively poor substrate for hepatic carboxylesterases and plasma cholinesterase (EC 3.1.1.8), and also a potent competitive inhibitor of the latter enzyme [116][121], In contrast, the unnatural enantiomer, (+)-(2S,3/ )-cocaine, is a good substrate for carboxylesterases and cholinesterase. Because hydrolysis is a route of detoxification for cocaine and its stereoisomers, such metabolic differences have a major import on their monooxygenase-catalyzed toxification, a reaction of particular effectiveness for (-)-cocaine. 

Strychnine, which is detoxified by microsomal monooxygenase action, is more toxic to animals on low-protein diets, whereas octamethylpyrophosphoramide, carbon tetrachloride, and heptachlor, which are activated by monooxygenases, are less toxic. Phase II reactions may also be affected by dietary protein levels. Chloramphenicol glu-curonidation is reduced in protein-deficient guinea pigs, although no effect is seen on sulfotransferase activity in protein-deficient rats. 

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