Oxidation synchronous

Very recently, considerable effort has been devoted to the simulation of the oscillatory behavior which has been observed experimentally in various surface reactions. So far, the most studied reaction is the catalytic oxidation of carbon monoxide, where it is well known that oscillations are coupled to reversible reconstructions of the surface via structure-sensitive sticking coefficients of the reactants. A careful evaluation of the simulation results is necessary in order to ensure that oscillations remain in the thermodynamic limit. The roles of surface diffusion of the reactants versus direct adsorption from the gas phase, at the onset of selforganization and synchronized behavior, is a topic which merits further investigation. 

A relationship between the redox state of an iron—sulfur center and the conformation of the host protein was furthermore established in an X-ray crystal study on center P in Azotobacter vinelandii nitroge-nase (270). In this enzyme, the two-electron oxidation of center P was found to be accompanied by a significant displacement of about 1 A of two iron atoms. In both cases, this displacement was associated with an additional ligation provided by a serine residue and the amide nitrogen of a cysteine residue, respectively. Since these two residues are protonable, it has been suggested that this structural change might help to synchronize the transfer of electrons and protons to the Fe-Mo cofactor of the enzyme (270). 

If a dimer of Co(III) is present then two one-equivalent oxidations of H02 can occur synchronously to give H" and O2 otherwise H02 is an intermediate. 

The synchronous departure of R- (as opposed to a two-step process) is supported by (i) the considerable effect on the rate of varying R and ( ) the isotope effect. R- can also be scavenged by bromoform giving RBr . As with nearly all oxidations by Co(III), these are characterised by large E values (19 to 23 kcal. mole ) and large A values (10 -10 l.mole . sec ). 

Melatonin secretion is synchronized to the light/dark (LD) cycle, with a nocturnal maximum (in young humans, about 200 pg/ml plasma) and low diurnal baseline levels (about 10 pg/ml plasma). Studies have supported the value of the exogenous administration of melatonin in circadian rhythm sleep disorders, insomnia, cancer, neurodegenerative diseases, disorders of the immune function, and oxidative damage (Karasek et al. 2002 Pandi-Perumal et al. 2005, 2006 Srinivasan et al. 2005a,b, 2006 Hardeland et al. 2006). 

The observation of pores in the anodic oxide with a density in the order of 1011 cnT2 [Agl] supports the so-called fluctuating pore model [Lel3]. This model assumes that randomly distributed pores in the oxides work as charge collecting centers, which lead to oscillations synchronized by the applied external electric field. It should be noted that the observed pore density corresponds well with the roughness at the oxide-electrolyte interface observed after the stress-induced transition of an anodic oxide, as shown in Fig. 5.5. 

Gutmark, E., T. P. Parr, and D. M. Hanson-Parr. 1995. Synchronized acoustic excitation of fuel and oxidizer for efficient combustion. 16th CEAS/AIAA Aeroacoustics Conference Proceedings. Munich, Germany. 

Transition into the Kolbe region at platinum is associated with the formation of an oxide layer. Acetate ions are believed to be more strongly adsorbed on this layer than is water. Conversion of water to oxygen is then suppressed in favour of the oxidation of acetate ions [59, 60. Electron transfer from acetate is synchronous with cleavage of the alkyl-carboxylate bond leaving adsorbed carbon dioxide and... 

White et al. have reported a rapid fluorimetric determination of chlorpromazine by an in situ photochemical oxidation [139]. Variable-angle synchronous scanning fluorescence spectroscopy has also been applied to the determination of chlorpromazine and its sulfoxide [140]. 

These studies demonstrate the general mechanism of synchronization of biochemical systems, which I expect to be operative in even more complex systems, such as the mitochondrial respiration or the periodic activity of the slime mold Dictyostelium discoideum. As shown in a number of laboratories under suitable conditions mitochondrial respiration can break into self-sustained oscillations of ATP and ADP, NADH, cytochromes, and oxygen uptake as well as various ion transport and proton transport functions. It is important to note that mitochondrial respiration and oxidative phosphorylation under conditions of oscillations is open for the source, namely, oxygen, as well as with respect to a number of sink reactions producing water, carbon dioxide, and heat. 

Manecke et al.16s synthesized a semiconducting polymeric complex which possessed both bis(ethylene-l,2-dithiolato)Cu(II) and a phthalocyanine-Cu(II)-type structure 54. This Cu complex exhibited high catalytic activity in the oxidative polymerization of XOH, about 50 times higher than that of pyridine-Cu. A synchronous four-electron-transfer mechanism was proposed for the catalysis of 54. The phthalo-cyanine-Cu(II) type structure of 54 is presumed to form a complex with molecular... 

Such a mechanism might play an important role in a metal-ion-catalyzed enzymic oxidation in vivo, in which metal ions work cooperatively 166. A synchronous four-electron-transfer requires a specific spatial arrangement which should be posable in a macromolecular environment. 

Oxidation of oxalic acid with dimethyl-V,V-dichlorohydantoin and dichloroisocya-nuric acid is of first order with respect to the oxidant. The order with respect to the reductant is fractional. The reactions are catalysed by Mn(II). Suitable mechanisms are proposed.129 A mechanism involving synchronous oxidative decarboxylation has been suggested for the oxidation of a-amino acids with l,3-dichloro-5,5-dimethylhydantoin.130 Kinetic parameters have been determined and a mechanism has been proposed for the oxidation of thiadiazole and oxadiazole with trichloroiso-cyanuric acid.131 Oxidation of two phenoxazine dyes, Nile Blue and Meldola Blue, with acidic chlorite and hypochlorous acid is of first order with respect to each of the reductant and chlorite anion. The rate constants and activation parameters for the oxidation have been determined.132... 

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