• Title/Summary/Keyword: Dehalogenation

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N-Alkylation of Primary Aromatic Amines Using Alkylhalide and Triethylamine (알킬할라이드와 Triethylamine을 이용한 일급 아로미틱 아민의 N-알킬레이션)

  • Kim, Ju-Hee;Park, Myung-Sook
    • YAKHAK HOEJI
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    • v.49 no.2
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    • pp.162-167
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    • 2005
  • Synthetic method for the selective N-monoalkylation of anilines using alkyl halides and triethylamine under room temperature was described. The corresponding N-alkyl anilines were obtained in good yields with minor quantities of dialkylated products. Anilines 2a-m and 3a-m were identified using NMR and IR. A series of 2a-m and 3a-m has been synthesized from aniline, toluidines, ethylanilines, aminoacetophenones, phenetidines. Formation of anilines was undertaken with dropping of alkylhalides at room temperature in methanol (or ethanol) for 3 hours~5 days. Selectivity on the monoalkylation was relatively high. Synthetic ratio of monoalkylated and dialkylated product was 94 : 6 in case of maximum monoalkylation.

Isolation of dhlA Gene Responsible for Degradation of 1, 2-dichloroethane from Metagenomic Library Derived from Daecheong Reservoir (대청호로부터 제작한 메타지놈 라이브러리에서 1, 2-dichloroethane의 분해에 관여하는 dhlA 유전자의 분리)

  • Kang, Cheol-Hee;Moon, Mi-Sook;Song, Ji-Sook;Lee, Sang-Mhan;Kim, Chi-Kyung
    • Korean Journal of Ecology and Environment
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    • v.38 no.2 s.112
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    • pp.137-145
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    • 2005
  • Traditional screening techniques have missed up to 99% of microbial resources existing in the nature. Strategies of direct cloning of environmental DNAs comprising tine genetic blueprints of entire microbial metagenomes provide vastly more genetic information than is contained in the culturable. Therefore, one way to screening the useful gene in a variety of environments is the construction of metagenomic DNA library. In this study, the water samples were collected from Daecheong Reservoir in the mid Korea, and analyzed by T-RFLP to examine the diversity of the microbial communities. The crude DNAs were extracted by SDS-based freezing-thawing method and then further purified using an $UltraClean^{TM}kit$ (MoBio, USA). The metagenomic libraries were constructed with the DNAs partially digested with EcoRI, BamHI, and SacII in Escherichia coli DH10B using the pBACe3.6 vector. About 14.0 Mb of metagenomic libraries were obtained with average inserts 13 ${\sim}$ 15 kb in size. The genes responsible for degradation of 1, 2-dichloroethane (1, 2-DCE) via hydrolytic dehalogenation were identified from the metagenomic libraries by colony hybridization. The 1, 2-dichloroethane dehalogenase gene (dhlA) was cloned and its nucleotide sequence was analyzed. The activity of the 1, 2-DCE dehalogenase was highly expressed to the substrate. These results indicated that the dhlA gene identified from the metagenomes derived from Deacheong Reservoir might be useful to develop a potent strain for degradation of 1, 2-DCE.

Effect of Minerals surface characteristics On Reduction Dehalogenation of chlorination solvents in water-FeS/FeS$_2$ system

  • 김성국;허재은;박세환;장현숙;박상원;홍대일
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2000.05a
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    • pp.108-111
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    • 2000
  • FeS/FeS$_2$ minerals have been known to be potentially useful reductant to the removal of common organic contaminants in groundwater and soil. This research is aimed at improving our understanding of factors affecting the pathways and rates of reductive transformation of Hexachloroethane by catalytical iron minerals in natural system. Hexachloroethane is reduced by FeS/FeS$_2$ minerals under anaerobic condition to tetrachloroethylene and trichloroethylene with pentachloroethyl radical as the intermediate products. The kinetics of reductive transformations of the Hexachloroethane have been investigated in aqueous solution containing FeS, FeS$_2$. The proposed reduction mechanism for the adsorbed nitrobenzene involves the electron donor-acceptor complex as a precursor to electron transfer. The adsorbed Hexachloroethane undergo a series of electron transfer, proton transfer and dehydration to achieve complete reduction. It can be concluded that the reductive transformation reaction takes place at surface of iron-bearing minerals and is dependent on surface area and pH. Nitrobenzene reduction kinetics is affected by reductant type, surface area, pH, the surface site density, and the surface charge. FeS/FeS$_2$-mediated reductive dechlorination may be an important transformation pathway in natural systems.

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Biochemical and molecular characterization of a tetrachloroethylene (PCE) dechlorinating Clostridium bifermentans DPH-1

  • Chang, Young-Cheol;Toyama, Tadashi;Kikuchi, Shintaro
    • Journal of environmental and Sanitary engineering
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    • v.23 no.2
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    • pp.1-18
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    • 2008
  • The tetrachloroethylene (PCE) dehalogenase of Clostridium bifermentans DPH-1 (a halorespiring organism) was purified, cloned, and sequenced. This enzyme is a homodimer with a molecular mass of ca. 70 kDa and exhibits dehalogenation of dichloroethylene isomers along with PCE and trichloroethylene (TCE). Broad range of substrate specificity for chlorinated aliphatic compounds (PCE, TCE, cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, 1,1-dichloroethylene, 1,2-dichloropropene, and 1,1,2-trichloroethane) for this enzyme was also observed. A mixture of propyl iodide and titanium citrate caused a light-reversible inhibition of enzymatic activity suggesting the involvement of a corrinoid cofactor. A partial sequence (81 bp) of the encoding gene for PCE dehalogenase was amplified and sequenced with degenerateprimers designed from the N-terminal sequence (27 amino acid residues). Southern analysis of C. bifermentans genomic DNA using the polymerase chain reaction product as a probe revealed restriction fragment bands. A 5.0 kb ClaI fragment, harboring the relevant gene (designated pceC) was cloned (pDEHAL5) and the complete nucleotide sequence of pceC was determined. The gene showed homology mainly with microbial membrane proteins and no homology with any known dehalogenase, suggesting a distinct PCE dehalogenase. So, C. bifermentans could play some important role in the initial breakdown of PCE and other chlorinated aliphatic compounds in sites contaminated with mixtures of halogenated substances.

Synthesis and Characterization of Polybenzimidazoles Containing Perfluorocyclobutane Groups for High-temperature Fuel Cell Applications

  • Chang, Bong-Jun;Kim, Dong-Jin;Kim, Jeong-Hoon;Lee, Soo-Bok;Joo, Hyeok-Jong
    • Korean Membrane Journal
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    • v.9 no.1
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    • pp.43-51
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    • 2007
  • This paper describes the preparation and characterization of two kinds of fluorinated polybenzimidazole (PBI)s which can be potentially used for phosphoric acid-doped, high-temperature polymer electrolyte membrane fuel cells. Two kinds of perfluorocyclobutane (PFCB)-containing monomers were prepared via following synthetic steps; after fluoroalkylation of methyl 3-(hydroxy) benzoate and methyl 4-(hydroxy) benzoate with 1,2-dibromotetrafluoroethane and subsequent Zn-mediated dehalogenation, these compounds were cyclodimerized at $200^{\circ}C$ affording the ester-terminated monomers containing PFCB ether groups. The synthesized intermediates and monomers were characterized using FT-IR, $^1H-NMR,\;^{19}F-NMR$, and mass spectroscopy. The fluorinated PBIs were then successfully prepared through the solution polycondensation of the monomers and 3,3'-diaminobenzidine in polyphosphoric acid. Compared with traditional PBI, the glass transition temperatures of the fluorinated PBIs were obtained at $262^{\circ}C\;and\;269^{\circ}C$ which are lower than that of PBI and their initial degradation temperatures were still high over $400^{\circ}C$ under nitrogen. The fluorinated PBIs showed higher d-spacing values and improved solubility in several organic solvents as well as phosphoric acid, which confirmed they could be good candidates for the high temperature fuel cell membranes.

Transformation Characteristics of Chlorinated Aliphatic Hydrocarbon (CAH) Mixtures in a Two-Stage Column: 1st Chemical Column Packed with Zinc Natural Ore and 2nd Biological Column Stimulated with Propane-Oxidizing Microorganisms (아연 광석과 프로판산화 미생물을 이용한 이단 고정상 반응기에서의 염소계 지방족 탄화수소 혼합물 분해 특성)

  • Son, Bong-han;Kim, Nam-hee;Hong, Kwang-pyo;Yun, Jun-ki;Lee, Chae-young;Kwon, Soo-youl;Kim, Young
    • Journal of Korean Society on Water Environment
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    • v.23 no.5
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    • pp.723-730
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    • 2007
  • This study was conducted to develop a combined method for remediating a Chlorinated Aliphatic Hydrocarbons (CAHs) mixtures-contaminated aquifer. The process is consist of two processes. A chemical process (1st) using natural zinc ores for reducing higher concentrations of CAH mixtures to the level at which biological process is feasible; and A biological process (2nd) using aerobic cometabolism for treating lower concentration of CAH mixtures (less than 1 mg/L). Natural zinc ore showed relatively high transformation capacity, average dehalogenation percentage, and the best economic efficiency in previously our study. To evaluate the feasibility of the process, we operated two columns in series (that is, chemical and biological columns). In the first column filled with natural zinc ore and sand, CAH mixtures were effectively transformed with more than 95% efficiency, the efficiency depends on the Empty Bed Contact Time (EBCT) and the mass of zinc ore packed. Scanning Electron Microscope (SEM), X-Ray Diffraction (XRD) analysis were performed to make sure whether natural zinc ore played an key role in the dechlorination of the CAH mixtures. The characteristics of zinc metal surface changed after exposure to CAHs due to oxidation of $Zn^0$ to $Zn^{2+}$. In the biological column injecting propane, DO and effluent of the chemical column, only 1,1,1-TCA was cometabolically transformed. Consequently, the combined process would be effective to remediate an aquifer contaminated with high concentrations of CAH mixtures.

Biocatalytic Production of Chiral Epoxides (생촉매를 이용한 광학활성 에폭사이드 생산)

  • 이은열;최원재;윤성준;김희숙;최차용
    • KSBB Journal
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    • v.14 no.3
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    • pp.291-296
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    • 1999
  • Chiral epoxides are key intermediates for the production of chiral pharmaceuticals, agrochemicals, and functional food additives. Chiral epoxides can be produced by either chemical or biological method. In biocatalytic production routes, chiral epoxides can be produced via epoxidations of prochiral alkenes by monooxygenase or peroxidase. Kinetic resolution of racemic epoxides using whole cells of bacteria or fungi might be commercially useful, since it is possible to obtain chiral epoxides with high optical purities from relatively cheap and readily avaiable racemic epoxides. Some bioprocesses already are commercially developed: the biocatalytic production of chiral epichlorohydrin via microbial stereospecific dehalogenation, and lipase-catalyzed enantioselective hydrolysis in a hollow fiber membrane bioreactor for the production of chiral methyl trans-3-(4-methoxyphenyl)glycidate. the intermediate for calcium antagonist diltiazem. The importance of biocatalytic production of chiral epoxides with several examples from literature are presented.

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