• Journal of Korean Society of Environmental Engineers
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• v.31 no.4
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• pp.278-286
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• 2009

In this study, four natural Mn oxides ($NMO_1-NMO_4$) was characterized using x-ray diffraction, scanning electron microscopy, and their removal efficiency for 1-naphthol (1-NP) in aqueous phase, using batch reactor, was investigated. The results were compared with one another and a synthetic manganese oxide, birnessite. The NMOs have a various Mn minerals including pyrolusite (${\beta}-MnO_2$), cryptomeltane (${\alpha}-MnO_2$) as well as birnessite (${\delta}-MnO_2$) depending on their sources, which results in different removal efficiencies (removals, kinetics) and reaction types (sorption or oxidative-transformation). The comparative study showed that $NMO_1$ (electrolytic Mn oxide) have a higher removal efficiency for 1-NP via oxidative-transformation compared to birnessite. The 1-NP removals by NMOs were followed by pseudo-first order reaction, and the surface area-normalized specific rate constants ($K_{surf},\;L/m^2$ min) determined were in order of $NMO_1(3.31{\times}10^{-3})$>${\delta}-MnO_2(1.48{\times}10^{-3}){\fallingdotseq}NMO_3(1.46{\times}10^{-3})$>$NMO_2(0.83{\times}10^{-3})$>$NMO_4(0.67{\times}10^{-3})$. From the solvent extraction experiments with the Mn oxide precipitates after reaction, it was observed that the oxidative-transformation rates of 1-NP were in order of $NMO_1{\fallingdotseq}{\delta}-MnO_2$>$NMO_3$>$NMO_4{\gg}NMO_2$ and the analysis of HPLC chromatogram and UV-Vis. absorption ratios ($A_{2/4}$, $A_{2/6}$) on the supernatant confirmed that the reaction products were oligomers formed by oxidative-coupling reaction. Results from this study proved that natural Mn oxide (except $NMO_2$) used in this experiment can be effectively applied for the removal of naphthols in aqueous phase, and the removal efficiencies are depending on the surface characters of the Mn oxides.

• Journal of Korean Society of Environmental Engineers
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• v.32 no.6
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• pp.547-554
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• 2010

In this study, new manganese oxide (i.e., black-birnessite) particles with nanostructures were prepared and its physico-chemical properties and oxidative-transformation efficiency on 1,4-naphthoquinine(1,4-NPQ) in the presence of reactive mediator was investigated. The results were also compared with that of the manganese oxide (i.e., brown-birnessite) particles synthesized by classical McKenzie method. Analysis of XRD and SEM data show that the particles are a single phase corresponding to a birnessite-based manganese oxide with cotton ball-like shapes containing nanofibers. In batch experiments, removals of 1,4-NPQ by the black-birnessite follows pseudo-first-order kinetics and the rate constant values obtained are greater about 2.3 times than that of the brown-birnessite in spite of its lower surface area (41.0 vs 19.80 $m^2/g$). The results can be explained by the higher crystallinity and nano structured features of the back-birnessite particles, which give higher reactivity for the removals of the quinone compound. HPLC analysis of the reaction products confirmed that the balck-birnessites removed 1,4-NPQ through cross-coupling reaction in the presence of catechol as a reactive mediator.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2001.04a
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• pp.45-48
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• 2001

The packed column experiments were conducted with a field soil, collected directly from the aquifer located at Bonchon industrial complex in K-city in order to characterize SOM reaction with ozone and to delineate the transformation of water soluble SOM after ozonation. As reaction time increased, water soluble organic matter increased, and this organic matter was in the range of 500∼1000 dalton. pH of extractants decreased with the increase of ozonation time. This Is because aromtic compounds in SOM were oxidized and carboxylic acid groups were formed. From the FT-IR spectra, the content of carboxylate increased as ozone injection time increased and hydroxyl group, which represents phenolic and alcoholic hydroxyl groups decreased. This is because oxidative ring fission formed carboxyl acid groups. This result provides a good agreement with pH decrease.

• Applied Chemistry for Engineering
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• v.27 no.6
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• pp.659-663
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• 2016

The efficiency of a heterogeneous ruthenium zirconia catalyst ($Ru(OH)_x/ZrO_2$) was demonstrated to the selective oxidative transformation of alkenes or alkynes. The scissions of C-C double bonds to aldehydes and triple bonds to diketones or carboxylic acids were carried out with (diacetoxyiodo)benzene as an oxidant under dichloromethane (5 mL)/water (0.5 mL) solvent system at $30^{\circ}C$ for wide range of substrates. The $Ru(OH)_x/ZrO_2$composite showed higher catalytic activity and selectivity than other ruthenium-based homogeneous or heterogeneous catalysts for the scission reaction. The catalyst exhibited a high mechanical stability, and no leaching of the metal was observed during the reaction. These features ensured the reusability of the catalyst for several times for the oxidative cleavage of unsaturated hydrocarbons.

• Journal of Korean Society of Environmental Engineers
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• v.33 no.6
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• pp.396-404
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• 2011

An investigation on the removals of PAH-quinone compounds, which are commonly produced from the biological and/or chemical treatments of PAH-contaminated soils, from the aqueous phase via birnessite (${\delta}-MnO_2$)-mediated oxidative transformation is described. It was demonstrated that acenaphthenequinone (APQ), p-PAH quinone can be removed via birnessite-mediated oxidative-coupling reactions, and anthraquinone (AQ) and 1,4-naphthoquinone (1,4-NPQ), o-PAH quinones were efficiently removed by birnessite-mediated cross-coupling reactions in the presence of catechol (CAT) as a reactive mediator. The removals of PAH-quinone compounds followed pseudo-first-order reactions, and the rate constant (k, $hr^{-1}$) for the removals of 1,4-NPQ under the experiment conditions (1,4-NPQ = 10 mg/L, CAT = 50 mg/L, ${\delta}-MnO_2$ = 1.0 g/L, pH 5, Reaction time = 6~96 hr) was 0.0426, which was about 4 times lower than that of APQ (0.173). With the observed pseudo-first order rate constants with respect to birnessite loadings under the same experimental conditions, the surface-normalized specific rate constant, $K_{surf}$, for 1,4-NPQ was determined to be $8.5{\times}10^{-4}L/m^2{\cdot}hr$. The analysis of the kinetic data with respect to birnessite loading indicated that the cross-coupling reactions of 1,4-NPQ consist of two different reaction steps over time and the results have also been discussed in terms of the reaction mechanisms.

• Journal of Soil and Groundwater Environment
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• v.14 no.1
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• pp.44-50
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• 2009

The occurrence of endocrine disrupting compounds (EDCs), chemicals that interfere with human hormone system, are increasing in the freshwater, waste water and subsurface as well. In this study, we determined the reactivity of three EDCs in the presence of birnessite. In aqueous phase, bisphenol A, 2,4-dichlorophenol and 17${\beta}$-estradiol, which possesses phenoxy-OH, were very rapidly transformed by birnessite: up to 99% of initial concentrations (50 mg/L for bisphenol A, 100mg/L for 2,4-dichlorophenol, and 1.5mg/L for 17${\beta}$-estradiol) were destroyed within 60 minutes. Especially, bisphenol A was the most reactive chemical, disappearing by 99% in a few minutes. The reaction occurred on the surface of birnessite, showing a linear increase of first-order kinetic constants with the increase of the surface area of birnessite. In soil slurry phase, the reactivity of birnessiteto EDCs was faster than in aqueous phase probably due to the cross coupling reaction of phenoxy radicals with soil organic matter. Considering the rapid transformation of the EDCs in the both phases, this oxidative cross coupling reaction mediated by birnessite would be an effective solution for the remediation of EDCs in environmental media, especially in soil.

• YAKHAK HOEJI
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• v.36 no.3
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• pp.250-254
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• 1992

Benzo[C]phenanthidine alkaloids were found to exhibit considerably strong antileukemic activies. These alkaloids have been shown to be biosynthesized from the corresponding alkaloids throung an oxidative $C_6-N$ bond cleavage followed by recyclization between $C_6\;and\;C_{13}$ position of the protoberberine. Recently we have achieved the biomimetic transformation of protoberberine alkaloid, berberine into benzo[C]phenanthridine alkaloid, chelerythrine.

• Journal of Korean Society of Environmental Engineers
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• v.35 no.4
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• pp.247-256
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• 2013

In this study, alginate beads containing birnessite (Bir-AB), a highly reactive oxidative catalyst for the transformation of phenolic compounds, was prepared and its 1-naphthol (1-NP) removal efficiency was investigated in a batch test. Based on scanning electron microscopy image, it can be inferred that the alginate gel cluster acts as a bridge which bind the birnessite particles together. Kinetic experiment with Bir-AB of different mixing ratios of birnessite to alginate (Bir : AG=0.25 : 1~1 : 1 w/w) indicate that pseudo-first order kinetic constants, $k(hr^{-1})$ for the 1-NP removals increased about 1.5 times when the birnessite mixing ratio was doubled. The removals of 1-NP was found to be dependent on solution pH and the pesudo-first order rate constants were increased from 0.331 $hr^{-1}$ at pH 10 to 0.661 $hr^{-1}$ at pH 4. The analysis of total organic carbon for the reaction solutions showed that a higher removal of dissolved organic carbon was achieved with Bir-AB as compared to birnessite. HPLC chromatographic analysis of the methanol extract after reaction of 1-NP with Bir-AB suggest that the reaction products could be removed through incorporation into the aliginate beads as a bound residue. Mn ions produced from the oxidative transformation of 1-NP by birnessite were also removed by sorption to Bir-AB. The Bir-AB was recovered quantitatively by simple filtration and was reused twice without significant loss of the initial reactivity.

• Proceedings of the Korean Society of Crop Science Conference
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• 2017.06a
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• pp.45-45
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• 2017

The Indian meal moth, Plodia interpunctella, is one of the most important pests of stored food in the food processing industry worldwide. To control the Indian meal moth, methyl bromide, phosphine, high carbon dioxide, sulfuryl fluoride and plant essential oil fumigation have been considered. However, these treatments have disadvantages. For example, depleting the ozone layer, showing resistance in insect, low control efficacy or need high cost for treatment. Chlorine dioxide ($ClO_2$) is strong disinfectant and insecticide. The gas caused a malfunction in enzymes. The oxidative stress induced by $ClO_2$ gas treatment damaged to a physiological system and all life stages of P. interpunctella. The gaseous $ClO_2$ is a convincing alternative to methyl bromide for controlling P. interpunctella. The gaseous $ClO_2$ was generated by a chlorine dioxide generator (PurgoFarm Co., Ltd., Hwasung, Korea). It generated highly pure $ClO_2$ gas and the gas blown out through a vent into a test chamber. Gas entry to the chamber was automatically controlled and monitored by a PortaSene II gas leak detector (Analytical Technology, Collegeville, PA, USA). The properly prepared eggs, larvae, pupae, and adults of P. interpunctella were used in this experiment. Data were analyzed using SAS 9.4. Percentage data were statistically analyzed after arcsine-root transformation. Analysis of variance was performed using general linear model, and means were separated by the least significant difference test at P < 0.05. Fumigation is an effective management technique for controlling all stages of P. interpunctella. We found that $ClO_2$ gas treatment directly effects on egg, larvae, pupae and adults of P. interpunctella. The gas treatment with proper concentration for over a day achieved 100 % mortality in all stages of P. interpunctella and short time treatment or low concentration gas treatment results showed that the egg hatchability, pupation rate, and adult emergency rate were lowered compare with untreated control. Also, abnormal pupae or adult rate were increased. Gaseous $ClO_2$ treatment induced insecticidal reactive oxygen species (ROS), and it resulted in fatal oxidative stress in P. interpunctella. Taken together, these results showed that exposure proper concentration and time of the gas control all stages of P. interpunctella by inducing fatal oxidative stress. Further studies will be required to apply the gas treatment under real-world condition and to understanding physiological reaction in P. interpunctella caused by oxidative stress.

• Asian-Australasian Journal of Animal Sciences
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• v.25 no.6
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• pp.818-823
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• 2012

Tall fescue (Festuca arundinacea Schreb.) is an important cool season forage plant that is not well suited to extreme heat, salts, or heavy metals. To develop transgenic tall fescue plants with enhanced tolerance to abiotic stress, we introduced an alfalfa Hsp23 gene expression vector construct through Agrobacterium-mediated transformation. Integration and expression of the transgene were confirmed by polymerase chain reaction, northern blot, and western blot analyses. Under normal growth conditions, there was no significant difference in the growth of the transgenic plants and the non-transgenic controls. However, when exposed to various stresses such as salt or arsenic, transgenic plants showed a significantly lower accumulation of hydrogen peroxide and thiobarbituric acid reactive substances than control plants. The reduced accumulation of thiobarbituric acid reactive substances indicates that the transgenic plants possessed a more efficient reactive oxygen species-scavenging system. We speculate that the high levels of MsHsp23 proteins in the transgenic plants protect leaves from oxidative damage through chaperon and antioxidant activities. These results suggest that MsHsp23 confers abiotic stress tolerance in transgenic tall fescue and may be useful in developing stress tolerance in other crops.