• Analytical Science and Technology
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• v.11 no.6
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• pp.460-468
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• 1998

Schiff base ligands such as $SOPDH_2$, $SNDH_2$, $EBNH_2$, and $PBNH_2$ and their Co(II) complexes such as [$Co(II)(SND)(H_2O)_2$], [$Co(II)(SOPD)(H_2O)_2$], [$Co(II)(EBN)(H_2O)$], and [$Co(II)(PBN)(H_2O)$] have been synthesized. The mole ratio of Shiff base ligand to cobalt(II) for the Co(II) complexes was found to be 1:1. Also these complexes have been configurated with hexa-coordination. Reduction of dioxygen was investigated by cyclic voltammetry at glassy carbon electrodes modified with Schiff base Co(II) complexes in 1 M KOH aqueous solution. At modified glassy carbon electrode with Schiff base Co(II) complexes, reduction peak current of oxygen was increased and peak potential was shifted to more positive direction compared to bare glassy carbon electrode. The electrokinetic parameters such as number of electron and exchange rate constant were calculated from the results of cyclic voltammogrms. The reduction of dioxygen at glassy carbon electrode has been $2e^-$ reaction pathway. Exchange rate constant at glassy carbon electrode modified with Co(II) complexes was increased 2~10 times compared to bare electrode.

• Journal of Microbiology and Biotechnology
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• v.11 no.5
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• pp.895-898
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• 2001

DNA sequence analysis of doxA from Streptomyces peucetius subsp. caesius ATCC 27952 revealed a $95\%$ amino acid identity with that of Streptomyces strain C5. DoxA from S. peucetius subsp. caesius ATCC 27952 encodes a peptide with both conserved heme-binding and dioxygen-binding motifs. Expression of this gene in S. lividans 1326 resulted in bioconversion of daunorubicin to doxorubicin.

• Analytical Science and Technology
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• v.8 no.4
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• pp.649-654
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• 1995

The reactivity of superoxide ion($O{_2}^{-.}$) with halogenated substrates is investigated by cyclic voltammetry and rotated ring-disk electrode method in aprotic solvents. The more positive the reduction potential of the substituted nitrile, the more facile is nucleophilic displacement by $O{_2}^{-.}$. The reaction rates of halogenonitriles with $O{_2}^{-.}$ vary according to the leaving-group propensity of halide (Br>Cl>F). The relative reaction rates of other substituted nitriles are in the order of electron-withdrawing propensity of the substituent group (CN> $C(O)NH_2$ >Ph, $CH_2CN$). The reaction of $O{_2}^{-.}$ with dihalocarbons indicates that five-membered rings can be rapidly formed by the cyclization of substrate and $O{_2}^{-.}$, and the relative rates of cyclization depend on the number of methylenic carbons {$Br(CH_2)_nBr$, [n=1<2<3>4>5]}. Mechanisms are proposed for the reaction of $O{_2}^{-.}$ with halogenated substrates.

• Journal of Photoscience
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• v.9 no.2
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• pp.412-414
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• 2002

Several peroxovanadium(V) complexes with an organic chelate ligand decompose spontaneously, depending on the nature of the chelate ligand. The self-decomposition reactions of the dinuclear peroxovanadium(V) complex with 2-oxo-l,3-diaminopropane-N,N,N',N'-tetraacetate (dpot) and the peroxovanadium(V) complexes with N-carboxymethylhistidinate (cmhist) and histamine-N,N-diacetate (histada) accompany the reduction of vanadium(V) to vanadium(IV). This implies that the peroxide anion acts as a reducing agent and thus the peroxide is oxidized in the decomposition process of the peroxovanadium(V) complexes. The oxidized dioxygen species have been characterized spectrophotometrically. Superoxide anion has been detected in 2-3 % yields using the reduction of cytochrome c method and chemiluminescence method utilized MCLA as a fluorescer. Singlet oxygen has also been detected in higher yields on the basis of chemiluminescence of tryptophan.

• KSBB Journal
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• v.29 no.1
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• pp.1-8
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• 2014

Tyrosinases catalyze the hydroxylation of monophenolic compounds and the conversion of o-diphenols to oquinones. The enzymes are mainly involved in the modification of tyrosine into L-3,4-dihydroxyphenyl-alanine (L-DOPA) and DOPA/DOPAquinone-drived intermolecular cross-linking, which play the key roles of pigmentation to the cells. It is ubiquitously distributed in microorganisms, plants, and animals all around the nature world. They are classified as copper- containing dioxygen activating enzymes; two copper ions are coordinated with six histidine residues in their active sites and they are distinguished as met-, deoxy-, and oxy-form depending on their oxidative states. Natural extraction and recombinant protein approaches have been tried to obtain practical amounts of the enzymes for industrial application. Tyrosinases have been widely applied to industrial and biomedical usages such as detoxification of waste water containing phenolic compounds, L-DOPA as a drug of Parkinson's disease, biomaterials preparation based on the cross-linking ability and biosensors for the detection of phenolic compounds. Therefore, this review reports the mechanism of tyrosinase, biochemical and structural features and potential applications in industrial field.

• Archives of Pharmacal Research
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• v.16 no.2
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• pp.89-93
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• 1993

Incubation of $S(-)-^3H$-nicotine with rabbit lung microsomes in the presence of dioxygen and NADPH results in the formation of metabolities that bind covalently to microsomal macro-molecules. The addition of cytochrome P-450 monooxygenase inhibitors, $\alpha$-methylbenzyl ami-nobenzotriazole and aroclor 1260, inhibited both (S)-nicotine metabolism and covalent binding. The relative rates of oxidation of nicotine $\Delta^{1',5'}$ iminium ion to continine indicates that lung $100,000\times{g}$ supematant catalyzed this oxidation approximately 18 times slower than that of liver system based on mg of protein, and increased covalent interactions. Since than that of liver system based on mg of protein, nd increased covalent interactions. Since the activity of lung iminium oxidase appears much lowr than the liver, it is tempting to speculate that localized concentrations of nicotine $\Delta^{1',5'}$ iminium ion in the lung will survive for a longer period of time. These results support that cytochrome P-450 catalyzed oxidation of nicotine leads to the formation of reactive nad electrophilic intemediates capable of chemical interactions with biomacromolecules.

• Bulletin of the Korean Chemical Society
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• v.9 no.5
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• pp.298-303
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• 1988

Kinetic studies on cupric ion ($Cu^{2+}$) oxidation of 1-benzyl- and 1-aryl-1,4-dihydronicotinamides (XNAH) in aqueous solution were performed. In the presence of dioxygen ($O_2$), the reaction followed first order kinetics with respect to both XNAH and $Cu^{2+}$. The oxidation reaction was found to be independent and parallel to the acid-catalyzed hydration reaction of XNAH. The catalytic role of $Cu^{2+}$ for the oxidation of XNAH in the presence of $O_2$ was attributed to $Cu^{2+}/Cu^+$ redox cycle by the reactions with XNAH and $O_2$. The second order rate constants of the Cu2+ oxidation reaction kCu, and acid-catalyzed hydration reaction $k_H$ were strongly dependent on the nature of the substituents in 1-aryl moiety. The slopes of log $k_{Cu}$ vs log $K_H$ and log $k_{Cu}$ vs ${\sigma}_p$ of the substituents plots were 1.64 and -2.2, respectively. This revealed the greater sensitivity of the oxidation reaction rate to the electron density on the ring nitrogen than the hydration reaction rate. A concerted two-electron transfer route involving XNAH-$Cu^{2+}$ complex was proposed for mechanism of the oxidation reaction.

• Journal of Ginseng Research
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• v.13 no.1
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• pp.98-104
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• 1989

In order to determine the specific active oxygen species directly related to chlorophyll bleaching in the leaf-burning disease, we investigated the effects of singlet oxygen (1O2), superoxide radical (O2-), and hydrogen Peroxide (H2O2) on isolated chloroplast suspension and leaf discs from Panax ginseng C.A. Meyer. When the singlet oxygen was added to the chloroplast suspension, the chlorophyll and carotenoid contents were decreased by more than 809), similar to treatment with high light intensity (100 KLux). We assumed that the conversion of dioxygen (O2) produced either in photolysis or in breakdown of hydrogen peroxide to singlet oxygen resulted from photorespiration. On the basis of these experiments , :he inhibitory effects of active oxygen scavengers propylgallic acid (PGA), 2,5-ditetrabutyl hydroquinon (DBH), sodium pyrosulfate (SPS), and ascorbic acid (ABS) were examined. In chloroplast suspension all four scavengers inhibited chlorophyll bleaching by more than 75fl , and in the leaf discs the inhibition rates of SPS, PGA and ABS were 46%, 51%, and 96% respectively.

• Journal of Plant Biotechnology
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• v.29 no.4
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• pp.229-233
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• 2002

Ferritin is ubiquitous in bacteria, animals and plants. Ferritin is thought to play two main roles in living cells to provide iron for the synthesis of iron protein such as ferretoxin and cytochromes and to prevent damage from radicals produced by iron/dioxygen interaction. To enhance the resistance of potato to Erwinia carotovora, the soybean ferritin gene was introduced into the potato either under CaMV 35S or hsr203J promoter. Potato transgenic plants were screened by PCR analysis using specific primers to the ferritin gene. Expression of ferritin gene under CaMV 35S and hsr203J promoter in potato transgenic plants was confirmed by northern blot analysis. hsr203J promoter known to pathogen inducible in tobacco drives the induction upon Phytophthora infestan in potato and the transcript level of ferritin gene was extremely high after 24 hours post inoculation. One of transformants under CaMV 35S promoter was increased 2.5 fold than untransformant. Each one of transgenic potato containing gene promoter CaMV 35S and hsr203J-ferrtin fusion exhibited tolerance against potato soft rot.

• Journal of the Korean Chemical Society
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• v.28 no.6
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• pp.384-392
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• 1984

Reaction of the Fe(II) complex of a fully saturated tetradentate macrocyclic ligand [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$, where [14]ane$N_4$ represents 1,4,8,11-tetraazacyclotetradecane, with $O_2$ has been investigated in acetonitrile solutions. [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$ reacts with oxygen to yield low spin Fe(III) species, [Fe([14]aneN$_4)(CH_3CN)_2]^{3+}$, which undergoes metal ion assisted oxidative dehydrogenation of the macrocyclic ligand to produce low spin Fe(II) complex, [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$. The macrocyclic ligand in [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$ is highly unsaturated and its double bonds are conjugated. [Fe([14]dieneN$_4)(CH_3CN)_2]^{2+}$ and [Fe([14]dieneN$_4)(CH_3CN)_2]^{3+}$ are isolated as the intermediates of the reaction. The Fe(II) complexes involved in this oxidative dehydrogenation reaction react with carbon monoxide to give respective carbon monoxide derivatives, [FeL$(CH_3CN)(CO)]^{2+}$ (where L = macrocyclic ligand). The values of $v_{CO}$ of [FeL$(CH_3CN)(CO)]^{2+}$, and the electrochemical oxidation potentials of Fe(II) ${\to}$ Fe(III) and the qualitative stability toward air-oxidation for [FeL(CH$_3CN_2)^{2+}$ increase as the degree of unsaturation of the macrocyclic ligands increase.