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The Ir(PPh$_3)_2\;(CO)OClO_3\;and\;Ir(PPh_3)_3N_2Cl$ Mediated Activation of Aldehyde C-H Bonds via Chelate-Assisted Oxidative Addition

  • Ko, Jae-Jung;Joo, Wan-Chul;Kong, Young-Kun
    • Bulletin of the Korean Chemical Society
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    • v.7 no.5
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    • pp.338-341
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    • 1986
  • Hydrocarbon solution of $Ir(PPh_3)_2(CO)OClO_3$ reacts with $Ph_2PC_6H_4$-o-CHO and 3-methyl-2-aminopyridinyl aldimine to yield ${\bar{Ir(Ph_2PC_6H_4-o-CO)}}\;(PPh_3)_2(CO)(H)ClO_4$(1) and ${\bar{Ir(NC_6H_6NC}}C_6H_5)(PPh_3)_2(CO)(H)ClO_4$(2), respectively. The compound $Ir(PPh_3)_2N_2Cl$ also reacts with $Ph_2PC_6H_4$-o-CHO and 3-methyl-2-aminopyridinyl aldimine to give ${\bar{Ir(Ph_2PC_6H_4-o-C}}O)(PPh_3)_2(H)Cl(3)$ and $Ir(NC_6H_5NCC_6H_5(PPh_3)_2(H)Cl(4)$, respectively. Compounds 1, 2, 3, and 4 were characterized by infrared, $^1H$ NMR, $^{31}p$ NMR, UV spectra, and conductivity measurements.

No Association of $CYP2D6^*4$ and $CYP2D6^*10$ Polymorphisms with Tardive Dyskinesia in Korean Schizophrenics (한국인 정신분열병 환자의 지연성 운동장애와 $CYP2D6^*4$$CYP2D6^*10$ 다형성들의 연합에 대한 고찰)

  • Woo, Sung-Il;Kang, Dong-Woo;Seo, Han-Gil;Kim, Bong-Jo;Lee, In-Sang;Jeong, Geun-Hoa;Park, So-Young;Jung, Chi-Yeong;Lee, Hwan-Cheol;Jeong, Kyeong-Cheon;Sohn, Jin-Wook
    • Korean Journal of Biological Psychiatry
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    • v.7 no.2
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    • pp.140-146
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    • 2000
  • P450 CYP2D6 enzyme(=debrisoquine hydroxylase) is known to metabolize many neuroleptics and some genetic polymorphisms in the CYP2D6 gene were reported to be associated with tardive dyskinesia(TD). We investigeted the association of two genetic polymorphisms in the CYP2D6 gene, $CYP2D6^*4$ and $CYP2D6^*10$, with TD in Korean schizophrenic subjects. Subjects consisted of 71 Korean schizophrenics and TD was evaluated using the Abnormal Involuntary Movement Scale (AIMS). There were no statistically significant differences in the demographic variables of age, male to female percentage and the current antipsychotic(CPZ equivalent) dose between the group with TD and the group without TD. But the duration of antipsychotic drug exposure was significantly higher in the group without TD(p=0.000, by independent t-test). The mean AIMS score in the group with TD was $11.2{\pm}6.6$(S.D.). Genotypings for the presence of $CYP2D6^*4$ and $CYP2D6^*10$ were done using PCR amplifications and endonuclease digestions. There were no statistically significant genotypic and alleleic associations between TD and $CYP2D6^*4$(by chisquare tests), and between TD and $CYP2D6^*10$(by chi-square tests). These results indicate that the $CYP2D6^*4$ and $CYP2D6^*10$ polymorphisms have no significant roles in the causation of TD.

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Synthesis and Spectroscopic Studies of Metal Complexes Formed in the Reaction of Metal Ions with Urea at High Temperature (높은 온도에서 Urea와 금속이온과의 반응으로 얻어진 금속 Complexes의 합성과 분광학적 연구)

  • Gaballa, Akmal S.;Teleb, Said M.;Nour, El-Metwally
    • Journal of the Korean Chemical Society
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    • v.51 no.4
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    • pp.339-345
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    • 2007
  • Urea reacts with PtCl2, H2[PtCl6]·6H2O, H2[IrCl6] and Ni(CH3CO2)2 in aqueous solution at high temperature (60-80 °C) yielding [PtCl2(Urea)]·2H2O (1), (NH4)2[PtCl6] (2), (NH4)2[IrCl6]·H2O (3) and [Ni2(OH)2(NCO)2(H2O)2] (4) complexes, respectively. In complex 1, urea coordinates to Pt(II) as a neutral bidentate ligand via amido nitrogen atoms. In complexes 2, 3 and 4 it seems that the coordinated urea molecules decompose during the reaction at high temperature and a variety of reaction products are obtained. All complexes were isolated in moderate yields as dark green (1), yellow (2), pale brown (3) and faint green (4) precipitates, respectively. The reaction products were characterized by their microanalysis, IR, 1H and 13C NMR spectra as well as thermal analysis. General mechanisms describing the formation of these complexes were suggested.

Growth and Yield Responses of Soybean to Overhead Flooding Duration at Four Growth Stages (관수시간에 따른 콩의 생육 및 수량반응)

  • 박경열;이종형;조영철
    • KOREAN JOURNAL OF CROP SCIENCE
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    • v.40 no.1
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    • pp.92-97
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    • 1995
  • The objective of this study is to investigate the growth characters of overhead flooded soybean plants at four growth stage. Overhead flooding treatments were applied at the vegetative growth stage ($V_3,\;V_6$) and the reproductive stage ($R_2,\;R_4$) for 6.12.24 hrs, respectively. Yield and yield components were more decreased as the overhead flooding duration was longer and the growth stage was later. Yield was not reduced significantly in soybean plants flooded at $V_3$ stage regardless of flooding duration, and flooded 6 or 12 hrs at $V_6$ stage. When compared to the control, 27 to 36% of yield reduction was observed in soybean plants flooded for 24 hrs at $V_6$ stage, 6 or 12 hrs at $R_2$ stage, and 6 hrs at $R_4$ stage. And 43%, 53% and 66% of yield were reduced through the flooding treatment for 24 hrs at $R_2$ stage 12 hrs and 24 hrs at $R_4$ stage, respectively. So yield reduction was higher in overhead flooded soybean plants at the reproductive stage than that at the vegetative growth stage.

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Effect of [6]-Gingerol on Bcl-2 and Bax Expression in MDA-MB-231 Human Breast Cancer Cell Line ([6]-Gingerol이 인체 유방암세포 MDA-MB-231에서 Bcl-2와 Bax 발현에 미치는 영향)

  • Seo, Eun-Young;Kim, Woo-Kyung
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.35 no.6
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    • pp.671-676
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    • 2006
  • We investigated the effect of gingerol (Zingiber officinale Roscoe, Zingiberaceae) on Bcl-2 and Bax expression in MDA-MB-231 human breast cell lines. The oleoresin from rhizomes of ginger contains [6]-gingerol (1-[4'-hydroxy-3'-methoxyphenyl]-5-hydroxy-3-decanone). We previously reported that [6]-gingerol inhibits cell proliferation in MDA-MB-231 human breast cancer cell lines. In this study, we examined protein and mRNA expression associated with cell apoptosis in MDA-MB-231 human breast cancer cell lines. We cultured MDA-MB-231 cells in presence of various concentrations 0, 2.5, 5 and $10\;{\mu}M$ of [6]-gingerol. Bcl-2 protein and its mRNA levels were decreased dose-dependently in cells treated with [6]-gingerol, but Bax protein and its mRNA levels were unchanged by [6]-gingerol treatment. Bcl-2/Bax ratio was decreased in a dose dependent manner treated with [6]-gingerol. Caspase-3 activity was significantly increased dose-dependently in cell treated with [6]-gingerol (p<0.05). In conclusion, we have shown that [6]-gingerol induces apoptosis in MDA-MB-231 human breast cancer cell lines.

Photochemical Hydrogen Evolution in K4Nb6O17 Semiconductor Particles Sensitized by Phosphonated Trisbipyridine Ruthenium Complexes

  • Jung, Young-Hee;Shim, Hyun-Kwan;Kim, Hyun-Woo;Kim, Yeong-Il
    • Bulletin of the Korean Chemical Society
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    • v.28 no.6
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    • pp.921-928
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    • 2007
  • Three different phosphonated trisbipyridine ruthenium complexes, [(4-CH3-4'-CH2PO(OH)2-2,2'-bipyridine)- (bpy)2Ru]·(PF6)2 (Ru-P1), [(4-CH3-4'-CH2PO(OH)2-2,2'-bipyridine)3Ru]·(PF6)2 (Ru-P2), and [(4,4'-CH2PO- (OH)2-2,2'-bipyridine)3Ru]·(PF6)2 (Ru-P3) were synthesized and their photochemical and electrochemical properties were studied. These ruthenium complexes were strongly adsorbed on the surface of the layered metal oxide semiconductor K4Nb6O17 that was partially acid-exchanged and sensitized up to pH 10, while the carboxylated ruthenium complex, (4,4'-COOH-2,2'-bipyridine)3Ru·Cl2 (Ru-C) that was previously studied was sensitized only below pH 4. The visible light water reduction at K4Nb6O17 that was internally platinized and sensitized by these phosphonated Ru-complexes was comparatively studied using a reversible electron donor iodide.

The Complexes of Iodobenzene with Halogens and Interhalogens in Carbon Tetrachloride (요오드벤젠과 할로겐 또는 할로겐間化合物 사이의 錯物에 관한 연구)

  • Choi, Sang-Up;Kim, Eung-Ryul
    • Journal of the Korean Chemical Society
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    • v.11 no.3
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    • pp.94-99
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    • 1967
  • The interactions of iodobenzene with iodine, iodine monobromide, iodine monochloride and chlorine in carbon tetrachloride solution have been investigated by means of ultraviolet spectrophotometric measurements. The results reveal the formation of one to one molecular complexes, $C_6H_5I{\cdot}I_2$, $C_6H_5I{\cdot}IBr$, $C_6H_5I{\cdot}ICl$, and $C_6H_5I{\cdot}Cl_2$, in solution. The equilibrium constants obtained at room temperature (about $21^{\circ}C$) for the formation of these four complexes are 0.23, 0.73, 1.2 and 0.070 l $mole^{-1}$, respectively. Comparison of these results with those reported in the literature on other complexes of similar type indicates that the relative stabilities of these complexes decrease in the following orders: ICl>IBr>$I_2$>$Br_2$>$Cl_2$ $C_6H_5I$>$C_6H_6$>$C_6H_5Br$>$C_6H_5Cl$>$C_6H_5F$.

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Theoretical Investigation for the Molecular Structure and Binding Energies of C6H6+-(H2O)n (n=1-5) Complexes (벤젠양이온-물 복합체[C6H6+-(H2O)n (n=1-5)]의 결합 에너지 및 분자 구조에 관한 이론적 연구)

  • Kim, Si-Jo;Kim, Seung-Joon
    • Journal of the Korean Chemical Society
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    • v.54 no.6
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    • pp.671-679
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    • 2010
  • The geometrical parameters and binding energies of the benzene ion-water complex [$C_6H_6^+-(H_2O)_n$(n=1-5)] have been investigated using ab initio (MP2) and density functional theory (DFT) with large basis sets. The harmonic vibrational frequencies and IR intensities are also determined to confirm that all the optimized geometries are true minima. Also zero-point vibrational energies have been considered to predict the binding energies. The predicted binding energy of 8.6 kcal/mol for $C_6H_6^+-(H_2O)$ at the MP2/aug-cc-pVTZ level of theory is in excellent agreement with recent experimental result of $8.5{\pm}1$ kcal/mol.

Effects of n-6/n-3 and P/S Ratio of Dietary Lipid on Thromboxane B2 and 6-Keto prostaglandin F1$\alpha$ Production in Rat (P/S 비율과 n-6/n-3 비율을 달리한 식이지방이 흰쥐의 Thromboxane B2 와 6-Keto prostaglandin F1$\alpha$ 합성에 미치는 영향 연구)

  • 김우경
    • Journal of Nutrition and Health
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    • v.27 no.6
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    • pp.574-582
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    • 1994
  • The effects of age and dietary fatty acid composition on prostagladin production was investigated in Sprague-Dawley strain male rats. Animals weighing 88.6$\pm$2.2g were fed 10% dietary fat(W/W, 20% of total energy). The P/S ratios of dietary lipid were three levels(0.5, 1, 2) and there were three different levels of n-6/n-3 fatty acid ratio(2, 4, 8) in each P/S ratio. The experimental period were 1 month and 12 months, respectively. The results of this study were as follows. As the age of rats increased, the plasma thromboxane B2 production increased, but aorta 6-keto prostaglandin F1$\alpha$ decreased. When a higher amount of n-3 fatty acid was fed in each P/S ratio, the relative percentage of linolenic acid and EPA in platelet increased.

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A Convenient Preparation of Polychloroanisidine and Fluorochloroanisole Derivatives (Polychloroanisidine 및 Fluorochloroanisole 유도체의 간편한 합성)

  • Kim, Yu Seon;Kim, Tae Yeong;Kim, Yun Hui
    • Journal of the Korean Chemical Society
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    • v.18 no.4
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    • pp.278-288
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    • 1974
  • Starting from p-dichlorobenzene, 2-amino-4-chloroanisole could be prepared via a nitration, a methoxylation, and subsequent reduction. The repeated chlorination of 2-amino-4-chloroanisole resulted 2-amino-3,4,5-trichloroanisole without any isomeric products. The chlorination of 4-chloro-2-nitroanisole could easily give 2,4-dichloro-6-nitroanisole but polychlorination of the product could not be achieved at the atmospherical pressure. The repeated chlorination of 2-amino-4,6-dichloroanisole could give 2-amino-3,4,5,6-tetrachloroanisole, The Schiemann reaction of 2-amino-4-chloroanisole and 2-amino-4,6-dichloroanisole could give 2-fluoro-4-chloroanisole and 2-fluoro-4,6-dichloroanisole, respectively. The repeated chlorination of these fluorochloroanisoles could give 2-fluoro-3,4,5,6-tetrachloroanisole. In each chlorination process, the components of products were examined by means of NMR spectrometry and the chlorination reaction was repeated without isolating each isomeric product. The feasibility of the present routes of preparations was discussed in respects to the conveniency of reaction conditions and respective overall yields of the processes.

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