Utilization of hydrogen peroxide

The great utility of hydrogen peroxide as a reagent for the conversion of sulphoxides to sulphones spurred the investigation of other peroxy-containing compounds. Probably the most commonly used species is peracetic acid which is formed by the reaction of acetic acid with hydrogen peroxide. In addition, other peroxy acids such as pertrifluoroacetic acid and m-chloroperbenzoic acid and hydroperoxides and hydrotrioxides are often used to convert sulphoxides to sulphones. 

The Germans used hydrogen peroxide of 80-85% concentration, alone or in mixtures with combustibles, as a fuel for the big V2 rockets during World War II. The utilization of hydrogen peroxide for rocket propulsion and the explosive properties of hydrogen peroxide and its mixtures will be discussed in later sections (pp. 299, 307). 

The existence of proteins such as Superoxide Dismutase and Catalase in aerobes often is cited in support of the conclusion that 02 - and HOOH are biological toxins. The present understanding of the biological utilization of hydrogen peroxide includes enzyme-facilitated processes that involve its disproportionation, the dehydrogenation of organic molecules, and the production of hypochlorous acid in neutrophils (equations 23-25). 

N. Mizumo, C. Nozaki, 1. Kiyoto, M. Misono, Highly efficient utilization of hydrogen peroxide for selective oxygenation of alkanes catalyzed by Diiron-substituted polyoxometalate precursor, J. Am. Chem. Soc. 120 (1998) 9267. 

K. Kamata, K. Yamaguchi, S. Hikichi, N. Mizuno, [[W=(O)(O2)2(H2O))2(p-O)] -Catalyzed epoxidation of allylic alcohols in water with high selectivity and utilization of hydrogen peroxide, Adv. Synth. Catal. 345 (2003) 1193. 

N. Mizuno, C. Nozaki, I. Kiyoto, M. Misono, Selective oxidation of alkenes catalyzed by di-iron-substituted silicotungstate with highly efficient utilization of hydrogen peroxide, f. Catal 182 (1999) 285. 

Oxidation of cyclohexane with hydrogen peroxide and a SiWio[Fe(H20)]20386 catalyst at 83°C for 96 h gave a 55 45 cyclohexanol/cyclohexanone mixture in 66% conversion with 95% utilization of hydrogen peroxide.301 If the time can be reduced and cheap hydrogen peroxide is available, this could replace the current relatively inefficient air oxidation of cyclohexane in the production of nylon. 

Boveris, A., Sies, H., Martino, E. E., Docampo, R., Turrens, J. F. and Stoppani, A. O. M. (1980) Deficient metabolic utilization of hydrogen peroxide in Trypanosoma cruzi. Biochem. 

The iron proteins play important roles in the physiological transport and storage of molecular oxygen, in the oxidative metabolism of a wide variety of compounds, in the hydroxylation of a number of metabolites, in electron transfer processes, in the decomposition or utilization of hydrogen peroxide, and in the transport and storage of iron. 

S. G. Huling and co-workers. Enhanced Bioremediation Utilic ng Hydrogen Peroxide as a Supplemental Source of Ouygen A Eaboratoy and Field Study,... 

Though we and others (27-29) have demonstrated the utility and the improved sensitivity of the peroxyoxalate chemiluminescence method for analyte detection in RP-HPLC separations for appropriate substrates, a substantial area for Improvement and refinement of the technique remains. We have shown that the reactions of hydrogen peroxide and oxalate esters yield a very complex array of reactive intermediates, some of which activate the fluorophor to its fluorescent state. The mechanism for the ester reaction as well as the process for conversion of the chemical potential energy into electronic (excited state) energy remain to be detailed. Finally, the refinement of the technique for routine application of this sensitive method, including the optimization of the effi-ciencies for each of the contributing factors, is currently a major effort in the Center for Bioanalytical Research. 

M.S. Lin and B.I. Jan, Determination of hydrogen peroxide by utilizing a cobalt(II)hexacyanoferrate-modified glassy carbon electrode as a chemical sensor. Electroanalysis 9, 340-344 (1997). 

How does nature prevent the release of hydrogen peroxide during the cytochrome oxidase-mediated four-electron reduction of dioxygen It would appear that cytochrome oxidase behaves in the same manner as other heme proteins which utilize hydrogen peroxide, such as catalase and peroxidase (vide infra), in that once a ferric peroxide complex is formed the oxygen-oxygen bond is broken with the release of water and the formation of an oxo iron(IV) complex which is subsequently reduced to the ferrous aquo state (12). Indeed, this same sequence of events accounts for the means by which oxygen is activated by cytochromes P-450. 

Our approach utilized the metals gold, platinum, then later gold, platinum, and nickel electroplated in succession because the catalytic decomposition of hydrogen peroxide reaction we tested was most efficiently catalyzed with platinum.After fabrication of the nanowires they were freed by removing the conductive silver backing with nitric acid and the sacrificial template with a strong base, sodium hydroxide. Then nanorods were washed with deionized water and ultracentrifuged to achieve a neutral pH. 

The application of CPO, HRP and CiP is limited to sterically unencumbered substrates and all these peroxidases produce the same absolute configuration of the chiral hydroperoxide. To overcome this limitation, the semisynthetic enzyme selenosubtilisin, a mimic for glutathione peroxidase, with the peptide framework of the serine protease subtilisin was developed by Bell and Hilvert. This semisynthetic peroxidase catalyzes the reduction of hydrogen peroxide and hydroperoxides in the presence of 5-mercapto-2-nitrobenzoic acid. It was utilized by Adam and coworkers and Schreier and coworkers for the kinetic resolution of racemic hydroperoxides (equation 17) . The results obtained were very promising. 

---