• Journal of the Korean Chemical Society
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• v.41 no.1
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• pp.22-46
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• 1997

Kinetic studies on nucleophilic substitution reaction of phenacyl bromide and phenacyl chloride with pyridines were conducted at 25℃ and 35℃ in methanol-acetonitrile solvents mixtures. It was shown that the reaction proceeds via an SN2 reaction mechanism based on the transition state parameters, ΔH≠ and ΔS≠ and Bro nsted β values. Quantum mechanical model predicted a product-like transition state, where bond-formation is much more progressed than bond breaking, upon changing the leaving group to that with a better leaving ability.

• The Transactions of The Korean Institute of Electrical Engineers
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• v.59 no.12
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• pp.2262-2267
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• 2010

In order to analyze the reason of wall blackening, which affect the decline of lifetime in a ceramic metal halide lamp, we carried out the deterioration of ceramic tubes by a change in operating conditions with arc tubes of two types of spherical and cylindrical, and we have confirmed the cause of wall blackening through the analysis of element composition and spectrum from SEM/EDS and spectrum analyzer. Wall blackening of tungsten was shown by sputtering from ignition in 20 minute on/off condition and wall blackening from chemical reaction between PCA wall and rare earth halides was shown significantly in a condition without on/off test. Especially, the wall blackening and the decline of luminous flux were reduced by inner convection in spherical type arc tube. Moreover, the color temperature and color coordinate were changed by reduction of emission spectrum of Dy which causes the chemical reaction with PCA wall.

• Journal of Microbiology and Biotechnology
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• v.24 no.6
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• pp.835-842
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• 2014

Haloperoxidase (HPO, E.C.1.11.1.7) is a metal-containing enzyme oxidizing halonium species, which can be used in the synthesis of halogenated organic compounds, for instance in the production of antimicrobial agents, cosmetics, etc., in the presence of halides and $H_2O_2$. To isolate and evaluate a novel non-metal HPO using a culture-independent method, a cassette PCR library was constructed from marine seawater in Japan. We first isolated a novel HPO gene from Pseudomonas putida ATCC11172 by PCR for constructing the chimeric HPO library (HPO11172). HPO11172 showed each single open-reading frame of 828 base pairs coding for 276 amino acids, respectively, and showed 87% similarity with P. putida IF-3 sequences. Approximately 600 transformants screened for chimeric genes between P. putida ATCC11173 and HPO central fragments were able to identify 113 active clones. Among them, we finally isolated 20 novel HPO genes. Sequence analyses of the obtained 20 clones showed higher homology genes with P. putida or Sinorhizobium or Streptomyces strains. Although the HPO A9 clone showed the lowest homology with HPO11172, clones in group B, including CS19, showed a relatively higher homology of 80%, with 70% identy. E. coli cells expressing these HPO chimeric genes were able to successfully bioconvert chlorodimedone with KBr or KCl as substrate.

• Journal of Korean Society for Atmospheric Environment
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• v.34 no.2
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• pp.244-258
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• 2018

We performed this study to investigate the spatial, seasonal, and daily variations of the concentrations of volatile organic compounds (VOCs) in Pohang, where large steel industrial complexes are located. Ambient air sampling was undertaken at 4 sites during 4 seasons. Each sample was taken for 4 hours continuously for 8 consecutive days per season at each site. Three sites were located within the Pohang city, but one as a control site in Gyeongju. A total of 72 individual VOCs were determined by thermal desorption coupled with GC/MS, including aliphatics, aromatics, carbonyls and halides. The most abundant VOC was toluene, being followed by ethylbenzene and xylenes. Benzene concentrations(c.a. 0.7 ppb) were found to be much lower than the national ambient standard of 1.5 ppb. Overall, the VOCs levels in Pohang appeared to be lower than other national industrial complexes in Korea such as Shiwha-Banwol, Yeosu-Gwangyang, Gumi, and Ulsan. This implies that steel industry may not give significant impacts on the atmospheric levels of VOCs as much as petrochemical, electronic, and/or textile industries, where large amounts of organic solvents are used.

• Journal of Integrative Natural Science
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• v.10 no.4
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• pp.175-191
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• 2017

In organic chemistry amide synthesis is performed through condensation of a carboxylic acid and an amine with releasing one equivalent of water via the corresponding ammonium carboxylate salt. This method is suffering from tedious processes and poor atom-economy due to the adverse thermodynamics of the equilibrium and the high activation barrier for direct coupling of a carboxylic acid and an amine. Most of the chemical approaches to amides formations have been therefore being developed, they are mainly focused on secondary amides. Direct carbonylations of tertiary amines to amides have been an exotic field unresolved, in particular direct carbonylation of trimethylamine in lack of commercial need has been attracted much interests due to the versatile product of N,N-dimethylacetamide in chemical industries and the activation of robust N-C($sp^3$) bond in tertiary amine academically. This review is focused mainly on carbonylation of trimethylamine as one of the typical tertiary amines by transition metals of cobalt, rhodium, platinum, and palladium including the role of methyl iodide as a promoter, the intermediate formation of acyl iodide, the coordination ability of trimethylamine to transition metal catalysts, and any possibility of CO insertion into the bond of Me-N in trimethylamine. In addition reactions of acyl halides as an activated form of acetic acid with amines are reviewed in brief since acyl iodide is suggested as a critical intermediate in those carbonylations of trimethylamine.

• Proceedings of the KWS Conference
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• 2002.10a
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• pp.76-81
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• 2002

The dramatic increase in the depth of a weld bead penetration has been demonstrated by welding a stainless steel in GTA (Gas-Tungsten-Arc) process with activating flux which consists of oxides and halides. However, there is no commonly agreed mechanism fer the effect of flux on the process. In order to make clear the mechanism, each behavior of the arc md the weld pool in GTA process with activating flux is observed in comparison with a conventional GTA process. A constricted anode root is shown in GTA process with the activating flux, whereas a diffuse anode root is shown in the conventional process. These anode roots are related strongly to metal vapor from the weld pool and the metal vapor is also related to temperature distributions on the weld pool surface. Furthermore, it is suggested that a balance between the Marangoni force and the drag force of the cathode jet should dominate the direction of re-circulatory flow in the weld pool. The electromagnetic force encourages the inward re-circulatory flow due to the constricted anode root in the case with flux. The difference in flow direction in the weld pool changes the geometry or depth/width ratio of weld bead penetration.

• Journal of the Korean Chemical Society
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• v.11 no.2
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• pp.45-50
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• 1967

Radio thin layer chromatography of organic halogen compounds by neutron irradiation technique was investigated for the purpose of identifying and separating the mixture of halogen compounds. It was found that various halides, organic acids, and aldehyde gave a distinct developing peak both in cases of individual compound and a mixture of two or three components when the samples were developed by solvent methanol. But poly chlorinated compounds and aromatic or alicyclic chlorides gave more than one component peak when the sample was developed after neutron irradiation. Rf value of each compound was distinct and reproducible. The procedures were described and validity of the present method is discussed.

• Journal of the Korean Chemical Society
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• v.27 no.1
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• pp.46-52
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• 1983

Selective reduction of halide (Br, I) with lithium borohydride in halogen compounds containing chloro, nitro, ester and nitrile groups was achieved satisfactorily. 1-Bromo-4-chlorobutane was reduced to 1-chlorobutane in 96% yield and the reduction of p-nitrobenzyl bromide gave p-nitrotoluene in 98% yield. However, the selectivity on the reduction of ethyl 3-iodopropionate and 4-bromobutyronitrile required the presence of equimolar pyridine to give good yield of ethyl propionate (93%) and n-butyronitrile (88%), respectively. In competitive reduction of 1-bromoheptane and 2-bromoheptane, lithium borohydride reduced 1-bromoheptane preferentially in the molar ratio of 93:7.

• Journal of the Korean Chemical Society
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• v.9 no.1
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• pp.23-28
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• 1965

Halogen exchanges between benzyl chloride and chloride ion have been studied in 90% ethanol-water mixture, and activation parameters in the exchange reaction have been determined; ${\Delta}H^{\neq}$ = 18. 50 Kcal and ${\Delta}S^{\neq}$ = -22. 09 e. u. Results indicated that the reaction proceeded via a typical bimolecular mechanism. The importance of nucleophilic ability of attacking anion in $S_N2$ process has been stressed giving some experimental evidence. The order of reactivity of halides in the exchange reaction is better explained with the Swain's nucleophilic parameter than with the bond dissociation energies.

• Bulletin of the Korean Chemical Society
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• v.32 no.9
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• pp.3239-3244
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• 2011

Dinuclear Ni(II)-thiophene halides, which contain linear bridging thienylenes, trans,trans-[$(PR_3)_2$(X)Ni-Y-Ni(X)$(PR_3)_2$] {X = Cl, Br; $H_2Y$ = 5,5'-dichloro-2,2'-bithiophene ($H_2bth$); $H_2tth$ = 5,5"-dichloro-2,2':5',2''-terthiophene ($H_2tth$)} were prepared by the oxidative addition of dihalobithiophene ($H_2bth$) or dihaloterthiophene ($H_2tth$) to [$Ni(COD)_2$] in the presence of tertiary phosphines. Subsequent reactions of $NaN_3$ with the dinuclear Ni(II)-thiophene chlorides gave the corresponding Ni(II)-azido complexes, trans,trans-[$(PR_3)_2(N_3)$Ni-Y-Ni$(N_3)(PR_3)_2$], whose reactivity toward trimethylsilyl pseudohalides such as trimethylsilyl isothiocyanates and cyanides was investigated. In addition, the reaction of trans-[$BrNi(PEt_3)_2-C_4H_2S-C_4H_2S$-CHO], a thienyl Ni(II) complex containing a terminal aldehyde group, with phosphonium ylide was examined.