• Applied Biological Chemistry
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• v.42 no.4
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• pp.330-335
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• 1999

Pentachlorophenol(PCP), which is very persistent in soil and water environment, was tried to detoxify with oxidoreductive catalysts(peroxidase, laccase, tyrosinase and birnessite). To find out detoxification of PCP, the transformation of PCP through oxidative coupling was investigated in the presence of various oxidoreductive catalysts. PCP incubated with peroxidase was significantly transformed, however, in case of tyrosinase, the transformation was negligible. Using peroxidase, the optimal reaction condition was pH 5.6 and $16^{\circ}C$. The transformation of PCP was very fast in initiation step until 30 min but, that was not observed after 180 min. The transformation of PCP was increased by increasing peroacidase amount. When the effect of humic monomer was investigated as co-substrate on the transformation of PCP, the transformation of PCP was mostly decreased in the incubation with peroxidase, laccase, and birnessite. The transformation of PCP, however, was slightly increased by the incubation with tyrosinase in the presence of humic monomers as co-substrate, except catechol. On the basis of the results obtained, it may be suggested that PCP is able to be effectively detoxified through oxidative coupling mediated with oxidoreductive catalysts.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2005.04a
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• pp.49-52
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• 2005

In this study, abiotic transformation of 1-naphthol via oxidative-coupling reaction was evaluated using Mn oxide which is ubiquitous in natural soils. The transformation of 1-naphthol catalyzed by synthetic birnessite $({\delta}-MnO_2)$ followed pseudo-lst order reaction, and the rate constants was in the range of $0.053{\sim}0.13\;min^{-1}$ with birnessite loadings of $12.5{\sim}50\;mg/20\;mL$. Since the oxidation of 1-naphthol was occurred on the reactive surface of the oxide particles, the rate constants with various birnessite loadings were correlated with birnessite surface area concentration. The correlation showed a strong linearity, which confirms the supposition of the surface reaction. From the correlation, therefore, the surface area normalized rate constant, $k_{surf}$, was determined to be 0.032 $L/m^2\;min$.

• Journal of Environmental Health Sciences
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• v.33 no.1 s.94
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• pp.63-67
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• 2007

Laccase catalyzes the oxidation and polymerization of aromatic compounds in the presence of molecular oxygen. The oxidative transformation of chlorophene with laccase was conducted in a closed, temperature controlled system. The optimal pH for transformation of chlorophene was proven to be about 5-6. As the temperature rose up to $55^{\circ}C$, the transformation of chlorophene increased. The chlorophene transformation was not enhanced in the presence of soluble polymers. The toxicity of the reaction mixture was increased two times than that of initial reaction mixture after the enzymatic treatment. ABTS has enhanced chlorophene transformation at 0.1 mM and showed negative linear relationship with residual chlorophene by the reaction.

• Journal of Korean Society of Environmental Engineers
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• v.28 no.5
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• pp.535-542
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• 2006

In this study, removals of 1-naphthol by oxidative-coupling reaction using birnessite, one of natural Mn oxides present in soil, was investigated in various experimental conditions(reaction time, Mn oxide loadings, pH, etc). Removal efficiency of 1-naphthol by birnessite was high in all the experimental conditions, and UV-vis. and mass spectrometric analyses on the supernatant after reaction confirmed that the reaction products were oligomers formed by oxidative-coupling reaction. Pseudo-first order rate constants, f, for the oxidative transformation of 1-naphthol by birnessite was derived from the kinetic experiments under various amount of birnessite loadings, and using the observed pseudo-first order rate constants with respect to birnessite loadings, surface area-normalized specific rate constant, $k_{surf}$ was also determined to be $9.31{\times}10^{-4}(L/m^2{\cdot}min)$ for 1-naphthol. In addition, the oxidative transformation of 1-naphthol was found to be dependent on solution pH, and the pseudo-first order rate constants were increased from 0.129 at pH 10 to 0.187 at pH 4.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2004.04a
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• pp.43-46
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• 2004

Explosive chemicals have been major soil and groundwater contaminants especially in the nations with active military activities. Of these explosives, 2,4,6-trinitrotoluene (TNT) is the most refractory one due to its structural characteristics. Although its efficient reduction by Fe(0) is well-known, the reduction products - mainly aminotoluenes - still possess toxicities to terrestrial biota, and are resistant to biological degradation. In this study, therefore, abiotic transformation of TNT reduction products via oxidative-coupling reaction was evaluated using Mn oxide which is ubiquitous in natural soils. The transformation efficiency is increased with the number of amino groups. Considering the very efficient reduction rate of TNT by Fe(0), Mn oxide can be successfully used for the removal of TNT reduction products.

• Journal of Korean Society of Environmental Engineers
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• v.27 no.5
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• pp.476-485
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• 2005

In this study, abiotic transformation of TNT reduction products via oxidative-coupling reaction was investigated using Mn oxide. In batch experiments, all the reduction products tested were completely transformed by birnessite, one of natural Mn oxides present in soil. Oxidative-coupling was the major transformation pathway, as confirmed by mass spectrometric analysis. Using observed pseudo-first-order rate constants with respect to birnessite loadings, surface area-normalized specific rate constants, $k_{surf}$, were determined. As expected, $k_{surf}$ of diaminonitrotoluenes (DATs) ($1.49{\sim}1.91\;L/m^2{\cdot}day$) are greater about 2 orders than that of dinitroaminotoluenes (DNTs) ($1.15{\times}10^{-2}{\sim}2.09{\times}10^{-2}\;L/m^2{\cdot}day$) due to the increased number of amine group. In addition, by comparing the value of $k_{surf}$ between DNTs or DATs, amino group on ortho position is likely to be more preferred for the oxidation by birnessite. Although cross-coupling of TNT in the presence of various mediator compounds was found not to be feasible, transformation of TNT by reduction using $Fe^0$ followed by oxidative coupling using Mn oxide was efficient, as evaluated by UV-visible spectrometry.

• Journal of Korean Society of Environmental Engineers
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• v.29 no.9
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• pp.989-996
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• 2007

In this study, abiotic transformation of 1-naphthol(1-NP) via oxidative-coupling reaction and its reaction products were investigated in the presence of Mn oxides. The reaction products were characterized for their relative polarity using solvent extraction experiment and reverse-phase HPLC, and for structure using CCMS and LC/MS, and for absorption characteristics using UV-Vis spectrometry. The reaction products present in aqueous phase were more polar than parent naphthol and comprised of 1,4-naphthoquinon(1,4-NPQ) and oligomers such as dimers and trimers. Hydrophilic component present in water phase after solvent$(CH_2Cl_2)$ extractions was identified as naphthol polymerized products having molecular weight(m/z) ranging from 400 to 2,000, and showed similar UV-Vis. absorption characteristics to that of foil fulvic acid. Transformation of 1,4-NPQ, which is non-reactive to Mn oxide, to the polymerized products via cross-coupling reaction in the presence of 1-NP was also verified. In this experimental conditions(20.5 mg/L, 1-NP, 2.5 g/L $MnO_2$, pH 5), the transformation of 1-NP into the oligomers and polymerized products were about 83% of initial 1-NP concentrations, and more than 30% of the reaction products was estimated to be water insoluble fractions, not extracted by $H_2O$ methanol. Results from this study suggest that Mn oxide-mediated treatment of naphthol contaminated soils can achieve risk reduction through the formation of oligomers md polymer precipitation.

• Journal of Korean Society of Environmental Engineers
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• v.37 no.2
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• pp.73-80
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• 2015

An investigation on the removals of tetracycline (TTC), which is a family of antibiotics widely founded in the environment, from the aqueous solution by birnessite(${\delta}-MnO_2$)-mediated oxidative transformation was described. This study also examined the potential effect of the naturally occurring substances, humic acid (HA) on the oxidative transformation. The experiment was carried out in various conditions (reaction time, Mn oxide loadings, pH) and in the presence of HA as a batch test. The removals of TTC followed pseudo-first order reactions, and rate constants (k, $hr^{-1}$) for the removals of TTC were constantly increased with decreasing pH from 0.98 (pH 9) to 2.97 (pH 3). The rate constants also increased about 1.3 times when the birnessite loading increased from 1 to 2 g/L. Presence of HA (5 mg-C/L, at $pH{\geq}6$) caused some enhancement in the removals of TTC as compared to the control, and also showed the removal efficiencies of TTC in the birnessite mediated systems (TTC=0.25 mM, ${\delta}-MnO_2=2.0g/L$, pH 6) increased with increasing HA concentrations (1~10 mg-C/L). The results obtained from the oxidative transformation of TTC and the effect of HA were discussed in terms of reaction characteristics and mechanism.

• Korean Journal of Plant Tissue Culture
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• v.28 no.2
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• pp.87-90
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• 2001

BcGRl gene encoding cytosolic glutathione reductase of Chinese cabbage (Brassica campestris var. Pekinensis cv. Seoul) was placed under the control of the CaMV 35S promoter and introduced into tobacco (Nicotiana tabacum L. cv. Samsun) via Agrobacterium-mediated transformation. T$_{0}$ 32 independent plants transformed with BcGRl gene were selected with kanamycin and they were confirmed by polymerase chain reaction (PCR) and Southern blot analysis. Northern blot analysis revealed that the constitutive expression of BcGRl gene and there was no relationship between the copy number of introduced gene and the levels of BcGRl transcripts.

• Korean Journal of Environmental Agriculture
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• v.17 no.3
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• pp.239-245
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• 1998

To investigate the formation of bound residue with soil organic materials by oxidative coupling, nitroaromatics and their reduced metabolites, the insecticide parathion and the herbicide asulam were incubated with oxidoreductase, laccase or horseradish peroxidase, in the presence or absence of humic monomers. Most of aminotoluenes and amino-nitrophenols were completely transformed while most of nitrotoluenes and nitrophenols remained unchanged by a lactase or horseradish peroxidase in the presence or absence of humic monomers. Amino-nitrotoluenes were not transformed without humic monomers, but the addition of various humic monomers caused a considerable difference in the transformation of amino-nitrotoluenes by a lactase or horseradish peroxidase. Amino-nitrotoluenes were most transformed in the presence of catechol, syringaldehyde and protocatechuic acid. The insecticide parathion with nitro group and its metabolite were not mostly transformed in the presence or absence of humic monomers. The herbicide asulam with amino group remained unchanged without humic monomers as well, but the stimulating effect on the transformation of asulam was caused by the addition of catechol, syringaldehyde, protocatechuic acid or caffeic acid with a lactase.