• Bulletin of the Korean Chemical Society
• /
• v.22 no.8
• /
• pp.909-913
• /
• 2001

The kinetics of oxidative decarboxylation of pyruvic acid and benzoylformic acid by peroxomonophosphoric acid (PMPA) in aqueous medium have been investigated. The reaction follows second order-first order each in PMPA and substrate concentration a t constant pH. The reactivity of different peroxo species in the oxidation has been determined. Activation energy and thermodynamic parameters have been computed. A plausible mechanism consistent with the observed results is proposed.

• Bulletin of the Korean Chemical Society
• /
• v.30 no.7
• /
• pp.1583-1587
• /
• 2009

The four dentate $N_2O_2$ Schiff base ligand of bis(2-hydroxyacetophenone)-1,2-propanediimine (BHAPN) and its manganese (III) complex were synthesized and identified by microanalysis, spectral data ($^1H$ NMR, MS, FT-IR and UV-Visible) and molar conductivity measurement. The mild and efficient homogeneous oxidative decarboxylation of some carboxylic acids by catalytic amount of this manganese (III) complex, using tetrabutylamonium periodate as a mild oxidant in chloroform at room temperature is reported. The catalyst used in this study showed good activity for the decarboxylation of the titled compounds.

• Bulletin of the Korean Chemical Society
• /
• v.28 no.7
• /
• pp.1151-1155
• /
• 2007

In a previous study, a catalyst (A) was discovered for oxidative decarboxylation of melanin-concentrating hormone (MCH). To explain the catalytic action and to predict the structure of a new catalyst with improved activity, docking simulations were carried out for the complex formed between A and MCH. The simulations suggested that the three terminal groups of A form a hydrophobic pocket and that van der Waals interactions between the hydrophobic pocket and MCH play a role in stabilizing the MCH-A complex. Consequently, a new catalyst (B) was designed and synthesized in expectation of improved catalytic activity resulting from enhanced van der Waals interactions. The new catalyst, however, showed slightly lower catalytic activity. Lack of the accurate solution structure of MCH may be one of the factors associated with difficulties in prediction of improvement in catalytic activity by purely theoretical means. The results, however, revealed that variation of the acyl portion of the hydroxyproline portion may lead to improved catalysts.

• Journal of the Korean Chemical Society
• /
• v.58 no.1
• /
• pp.17-24
• /
• 2014

The oxidative decarboxylation of phenylsulfinylacetic acid (PSAA) by Cr(VI) in 20% acetonitrile -80% water (v/v) medium follows overall second order kinetics, first order each with respect to [PSAA] and [Cr(VI)] at constant [$H^+$] and ionic strength. The reaction is acid catalysed, the order with respect to [$H^+$] is unity and the active oxidizing species is found to be $HCrO_3^+$. The reaction mechanism involves the rate determining nucleophilic attack of sulfur atom of PSAA on chromium of $HCrO_3^+$ forming a sulfonium ion intermediate. The intermediate then undergoes ${\alpha}$,${\beta}$-cleavage leading to the liberation of $CO_2$. The product of the reaction is found to be methyl phenyl sulfone. The operation of substituent effect shows that PSAA containing electron-releasing groups in the meta- and para-positions accelerate the reaction rate while electron withdrawing groups retard the rate. An excellent correlation is found to exist between log $k_2$ and Hammett ${\sigma}$ constants with a negative value of reaction constant. The ${\rho}$ value decreases with increase in temperature evidencing the high reactivity and low selectivity in the case of substituted PSAAs.

• Bulletin of the Korean Chemical Society
• /
• v.21 no.12
• /
• pp.1254-1256
• /
• 2000

• Bulletin of the Korean Chemical Society
• /
• v.19 no.6
• /
• pp.615-616
• /
• 1998

• Korean Journal of Pharmacognosy
• /
• v.37 no.1 s.144
• /
• pp.60-66
• /
• 2006

Norditerpene alkaloids are the main toxic principles of traditional oriental herb 'chuawu(bu-shi),' which have been used in Chinese materia medica mainly for the treatment of musculoskeletal disorders. They are biosynthesized via cyclization of geranylgeranyl pyrophosphate, incoration of 2-aminoethanol and decarboxylation not via amino acid pathway, and the structural characteristics have tempted several oxidative reactions. In this study various norditerpene alkaloids were subjected to react active manganese dioxide and oxoammonium salt as oxidants. The oxidation was proceeded as dealkylation with aconitine type and dehydrogenations with lycoctonin and heteratisine type.

• Journal of Microbiology and Biotechnology
• /
• v.22 no.5
• /
• pp.668-673
• /
• 2012

Biohydrogen production from organic wastewater by anaerobically activated sludge fermentation has already been extensively investigated, and it is known that hydrogen can be produced by glucose fermentation through three metabolic pathways, including the oxidative decarboxylation of pyruvic acid to acetyl-CoA, oxidation of NADH to $NAD^+$, and acetogenesis by hydrogen-producing acetogens. However, the exact or dominant pathways of hydrogen production in the anaerobically activated sludge fermentation process have not yet been identified. Thus, a continuous stirred-tank reactor (CSTR) was introduced and a specifically acclimated acidogenic fermentative microflora obtained under certain operation conditions. The hydrogen production activity and potential hydrogen-producing pathways in the acidogenic fermentative microflora were then investigated using batch cultures in Erlenmeyer flasks with a working volume of 500 ml. Based on an initial glucose concentration of 10 g/l, pH 6.0, and a biomass of 1.01 g/l of a mixed liquid volatile suspended solid (MLVSS), 247.7 ml of hydrogen was obtained after a 68 h cultivation period at $35{\pm}1^{\circ}C$. Further tests indicated that 69% of the hydrogen was produced from the oxidative decarboxylation of pyruvic acid, whereas the remaining 31% was from the oxidation of NADH to $NAD^+$. There were no hydrogen-producing acetogens or they were unable to work effectively in the anaerobically activated sludge with a hydraulic retention time (HRT) of less than 8 h.

• BMB Reports
• /
• v.28 no.1
• /
• pp.12-16
• /
• 1995

The branched-chain ${\alpha}$-keto acid dehydrogenase (BCKAD) complex is a rate limiting enzyme which catalyzes the oxidative decarboxylation of branched-chain ${\alpha}$-keto acids. Numerous studies have suggested that BCKAD is subject to covalent modification in vitro via phosphorylation and dephosphorylation, which are catalyzed by a specific kinase and phosphatase, respectively. The biggest difficulty in the assay of BCKAD activity is to arrest the interconversion between the active and inactive forms. BCKAD activity was determined from fresh rat heart and liver tissues using homogenizing and assay buffers containing inhibitors of phosphatase and kinase. The results suggest that a radiochemical assay using ${\alpha}$-keto[1-$^{14}C$]-isovalerate as a substrate for the enzyme can be applied as a reliable method to determine in vitro enzyme activity with arrested interconversion between the active and inactive forms of the BCKAD complex.

• Journal of Microbiology
• /
• v.38 no.2
• /
• pp.53-61
• /
• 2000

Hydroxybenzoic acids are the most important intermediates in the degradative pathways of various aromatic compounds. Microorganisms catabolize aromatic compounds by converting them to hydroxylated intermediates and then cleave the benzene nucleus with ring dioxygenases. Hydroxylation of the benzene nucleus of an aromatic compound is an essential step for the initiation and subsequent disintegration of the benzene ring. The incorporation of two hydroxyl groups is essential for the labilization of the benzene nucleus. Monohydroxybenzoic acids such as 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, and 4-hydrosybenzoic acid, opr pyrocattechuic acid that are susceptible for subsequent oxygenative cleavage of the benzene ring. These terminal aromatic intermediates are further degraded to cellular components through ortho-and/or meta-cleavage pathways and finally lead to the formation of constituents of the TCA cycle. Many groups of microorganisms have been isolated as degraders of hydroxybenzoic acids with diverse drgradative routes and specific enzymes involved in their metabolic pahtway. Various microorganisms carry out unusual non-oxidative decarboxylation of aromatic acids and convert them to respective phenols which have been documented. Futher, Pseudomonas and Bacillus spp. are the most ubiquitous microorganisms, being the principal components of microflora of most soil and water enviroments.