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Synthesis and Characterization of a Di-$\mu$-oxo-bridged Molybdeum(V) Complexes (두 개 산소가교형 몰리브덴(V) 착물의 합성과 그 성질에 관한 연구)

  • Doh, Gil Myung;Kim, Ill Chool;Choi, Bo Yong
    • Journal of the Korean Chemical Society
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    • v.39 no.3
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    • pp.198-203
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    • 1995
  • The Mo(V) $di-\mu-oxo$ type $(Mo_2O_4(H_2O)_2L)$ complexes $(L:\;C_3H_7CH(SCH_2COOH)_2,\;C_6H_5CH(SCH_2COOH)_2,\;CH_3OC_6H_4CH(SCH_2COOH)_2,\;C_5H_{10}C(SCH_2COOH)_2,\;C_3H_7C(CH_3)(SCH_2COOH)_2,\;C_3H_7CH(SCH_2CH_2COOH)_2,\;C_6H_5CH(SCH_2CH_2COOH)_2)$ have been prepared by the reaction of $[Mo_2O_4(H_2O)_6]^{2+}$ with a series of dithiodicarboxy ligands. These complexes are completed by two terminal oxygens arranged trans to one another and each ligand forms a chelate type between two molybdenum. In $Mo_2O_4(H_2O)_2L$, two $H_2O$ coordinated at trans site of terminal oxygens. The prepared complexes have been characterized by elemental analysis, infrared spectra, electronic spectra, and nuclear magnetic resonance spectra. In the potential range -0.00 V to -1.00 V at a scan rate of 20 $mVs^{-1}$, a cathodic peak at -0.50∼-0.58 V (vs. SCE) and an anodic peak at -0.40∼-0.43 V (vs. SCE) have been observed in aquous solution. The ratio of the cathodic to anodic current ($I_{pc}/I_{pa}$) is almost 1, we infer that redox is reversible reaction.

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M.O. Studies of Configuration and Conformation (Part II) Configuration and Conformation of Ketimine isomers

  • Kim, Shi-Choon;Chun, Young-Gu;Lee, Ikchoon
    • Nuclear Engineering and Technology
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    • v.9 no.1
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    • pp.39-44
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    • 1977
  • The configuratior and conformation of N-methyl-C-phenylalkyl-ketimine isomers, Ph-CR=N$CH_3$ (R=H, $CH_3$, $CH_3$CH$_2$), have been studied from extended Huckel molecular orbital calculations. The result shows that the E-configuration of the C=N double bond is favored compared with that of the Z-configuration. The most preferable conformation of the phenyl ring rotamer in N-methyl-C-phenylaldimine and N-methyl-C-phenylmethylketimine are the coplanar forms with regard to the C=N plane, but the conformation of the $CH_3$CH$_2$-rotamer, in N-methyl-C-phenylethyl-ketimine, the gauche form (dihedral angle between C=N and $CH_3$CH$_2$- plane=90$^{\circ}$) is favored.

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Mechanistic Aspects in the Grignard Coupling Reaction of Bis(chloromethyl)dimethylsilane with Trimethylchlorosilane

  • 조연석;유복렬;안삼영;정일남
    • Bulletin of the Korean Chemical Society
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    • v.20 no.4
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    • pp.422-426
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    • 1999
  • The Grignard reactions of bis(chloromethyl)dimethylsilane (1) with trimethylchlorosilane (2) in THF give both the intermolecular C-Si coupling and intramolecular C-C coupling products. At beginning stage, 1 reacts with Mg to give the mono-Grignard reagent ClCH2Me2SiCH2MgCl (1) which undergoes the C-Si coupling reaction to give MC2Si(CH2SiMe3)2 3, or C-C coupling to a mixture of formula Me3SiCH2(SiMe2CH2CH2)nR1 (n = 1, 2, 3, ..; 4a, R1I = H: 4b, R1 = SiMe3). In the reaction, two reaction pathways are involved: a) Ⅰ reacts with 2 to give Me3SiCH2SiMe2CH2Cl 6 which further reacts with Mg to afford a Me2SiCH2Mel-SiCH2MgCl (Ⅱ) or b) I cyclizes intramolecularly to a silacyclopropane intermediate A, which undergoes a ring-opening polymerization by the nucleophilic attack of the intermediates I or Ⅱ, followed by the termination reaction with H2O and 2, to give 4a and 4b, respectively. As the mole ratio of 2/1 increased from 2 to 16 folds, the formation of product 3 increased from 16% to 47% while the formation of polymeric products 4 was reduced from 60% to 40%. The intermolecular C-Si coupling reaction of the pathway a becomes more favorable than the intramolecular C-C coupling reaction of the pathways b at the higher mole ratio of 2/1.

Synthesis and Structure of trans$[FeH(NCCH_2CH_2CH_2Cl)(dppe)_2]^+[BF_4]^-$ ($[FeH(NCCH_2CH_2CH_2Cl)(dppe)_2]^+[BF_4]^- $착물의 합성 및 구조)

  • 이재경;이순원
    • Korean Journal of Crystallography
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    • v.9 no.2
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    • pp.107-113
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    • 1998
  • Ar하에서 trans-FeHCl(dppe)2, 1을 4-chlorobutyronitrile에 녹이면, 착물 trans-[FeH(NCCH2CH2CH2Cl)(dppe)2]Cl, 2가 생성되고, 2는 NaBF4와 반응하여 착물 trans-[FeH(NCCH2CH2CH2Cl)(dppe)2][BF4], 3로 변환된다. 착물 3의 결정학 자료: 단사정계 공간군 P21/c, a=13.540(2) , b=17.058(3) , c=21.853(4) , β=90.15(1)o, Z=4, R(wR2)=0.0524(0.1239).

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Synthesis and Molecular Structures of $2-SC_4H_3CH=NN(H)C_6H_5 and (GaMe_2)_2(2-SC_4H_3CH=NNC_6H_5)_2$ ($2-SC_4H_3CH=NN(H)C_6H_5$$(GaMe_2)_2(2-SSC_4H_3CH=NNC_6H_5)_2$의 합성과 분자 구조)

  • 박권일;김용기;조성일
    • Korean Journal of Crystallography
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    • v.11 no.1
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    • pp.46-51
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    • 2000
  • The molecular structures of 2-SC₄H₃CH=NN(H)C/sub 6/H/sub 5/(C/sub 11/H/sub 10/N₂S) and (GaMe₂)₂(2-SC₄H₃CH=NNC/sub 6/H/sub 5/)₂(C/sub 26/H/sub 30/Ga₂N₄S₂) have been determined by X-ray diffraction. Crystallographic data for 2-SC₄H₃CH=NN(H)C/sub 6/H/sub 5/:orthorhombic space group P2₁2₁2₁, a=6.108(1)Å, b=7.593(1)Å, c=22.356(2)Å, V=1037.1(3)ų, Z=4, R=0.0613. Crystallographic data for (GaMe₂)₂(2-SC₄H₃CH=NNC/sub 6/H/sub 5/)₂:monoclinic space group P2₁/n, a=15.996(2) Å, c=9.879(3)Å, β=100.07.(2)°, V=2764.599)ų, Z=4, R=0.0503.

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Gas Sensing Characteristics and Preparation of SnO2 Nano Powders (SnO2 나노 분말의 합성 및 가스 감응 특성)

  • Lee, Ji-Young;Yu, Yoon-Sic;Yu, Il
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.24 no.7
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    • pp.589-593
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    • 2011
  • [ $SnO_2$ ]nano powders were prepared by solution reduction method using tin chloride($SnCl_2{\cdot}2H_2O$), hydrazine($N_2H_4$) and NaOH. The $SnO_2$ thick films for gas sensors were fabricated by screen printing method on alumina substrates and annealed at $300^{\circ}C$ in air, respectively. XRD patterns of the $SnO_2$ nano powders showed the tetragonal structure with (110) dominant orientation. The particle size of $SnO_2$ nano powders at the ratio of $SnCl_2:N_2H_4$+NaOH= 1:6 was about 60 nm. The sensing characteristics were investigated by measuring the electrical resistance of each sensor in a test box. Sensitivity of $SnO_2$ gas sensor to 5 ppm $CH_4$gas and 5 ppm $CH_3CH_2CH_3$ gas was investigated for various $SnCl_2:N_2H_4$+NaOH proportion. The highest sensitivity to $CH_4$ gas and $CH_3CH_2CH_3$ gas of $SnO_2$ sensors was observed at the $SnCl_2:N_2H_4$+NaOH= 1:8 and $SnCl_2:N_2H_4$+NaOH= 1:6, respectively. Response and recovery times of $SnO_2$ gas sensors prepared by $SnCl_2:N_2H_4$+NaOH= 1:6 was about 40 s and 30 s, respectively.

Seasonal Change of Rice-mediated Methane Emission from a Rice Paddy under Different Water Management and Organic Amendments (물 관리와 유기물 시용이 다른 논에서 벼 식물체를 통한 메탄 배출의 계절변화)

  • Shin, Yong-Kwang;Lee, Yang-Soo;Ahn, Jong-Woong;Koh, Mun-Hwan;Eom, Ki-Cheol
    • Korean Journal of Soil Science and Fertilizer
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    • v.36 no.1
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    • pp.41-49
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    • 2003
  • Methane emission was measured in a rice paddy under different water management and organic amendments. Methane emission from planted chambers and unplanted chambers was monitored to evaluate the rice-mediated methane emission. In flooding methane emission from planted chambers with NPK, NPK(+P), was $0.174g\;CH_4\;m^{-2}\;d^{-1}$ while that from unplanted chambers with NPK, NPK(-P), was $0.046g\;CH_4\;m^{-2}\;d^{-1}$ Methane emission from planted chambers with rice straw compost amendment, RSC(+P), was $0.214g\;CH_4\;m^{-2}\;d^{-1}$, while that from unplanted chambers with rice straw compost amendment, RSC(-P), was $0.076g\;CH_4\;m^{-2}\;d^{-1}$. Methane emission from planted chambers with rice straw amendment in Fehruary, RS2(+P), was $0.328g\;CH_4\;m^{-2}\;d^{-1}$, while that from unplanted chambers with rice straw amendment in February, RS2(-P), was $0.1g\;CH_4\;m^{-2}\;d^{-1}$. Methane emission from planted chambers with rice straw amendment in May, RS5(+P), was $0.414g\;CH_4\;m^{-2}\;d^{-1}$, while that from unplanted chamhers with rice straw amendment in May, RS5(-P), was $0.187g\;CH_4\;m^{-2}\;d^{-1}$. In intermittent irrigation methane emission from NPK(+P) was $0.115g\;CH_4\;m^{-2}\;d^{-1}$, while that from NPK(-P) was $0.041g\;CH_4\;m^{-2}\;d^{-1}$. Methane emission from RSC(+P) was $0.137g\;CH_4\;m^{-2}\;d^{-1}$, while that from RSC(-P) was $0.06g\;CH_4\;m^{-2}\;d^{-1}$. Methane emission from RS2(+P) was $0.204g\;CH_4\;m^{-2}\;d^{-1}$, while that from RS2(-P) was $0.09g\;CH_4\;m^{-2}\;d^{-1}$. Methane emission from RS5(+P) was $0.273g\;CH_4\;m^{-2}\;d^{-1}$, while that from RS5(-P) was $0.13g\;CH_4\;m^{-2}\;d^{-1}$. Methane transport via rice plant under flooding for NPK plot, RSC plot, RS2 plot and RS5 plot was 73.6%, 64.5%, 69.5% and 54.8%, respectively, and mean was 65.6%. Methane transport via rice plants under intermittent irrigation for NPK plot, RSC plot, RS2 plot and RS5 plot was 64.3%, 59.2%, 55.9% and 52.4%, respectively, and mean was 58.0%.

Evaluations of Spectral Analysis of in vitro 2D-COSY and 2D-NOESY on Human Brain Metabolites (인체 뇌 대사물질에서의 In vitro 2D-COSY와 2D-NOESY 스펙트럼 분석 평가)

  • Choe, Bo-Young;Woo, Dong-Cheol;Kim, Sang-Young;Choi, Chi-Bong;Lee, Sung-Im;Kim, Eun-Hee;Hong, Kwan-Soo;Jeon, Young-Ho;Cheong, Chae-Joon;Kim, Sang-Soo;Lim, Hyang-Sook
    • Investigative Magnetic Resonance Imaging
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    • v.12 no.1
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    • pp.8-19
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    • 2008
  • Purpose : To investigate the 3-bond and spatial connectivity of human brain metabolites by scalar coupling and dipolar nuclear Overhauser effect/enhancement (NOE) interaction through 2D- correlation spectroscopy (COSY) and 2D- NOE spectroscopy (NOESY) techniques. Materials and Methods : All 2D experiments were performed on Bruker Avance 500 (11.8 T) with the zshield gradient triple resonance cryoprobe at 298 K. Human brain metabolites were prepared with 10% $D_2O$. Two-dimensional spectra with 2048 data points contains 320 free induction decay (FID) averaging. Repetition delay was 2 sec. The Top Spin 2.0 software was used for post-processing. Total 7 metabolites such as N-acetyl aspartate (NAA), creatine (Cr), choline (Cho), lutamine (Gln), glutamate (Glu), myo-inositol (Ins), and lactate (Lac) were included for major target metabolites. Results : Symmetrical 2D-COSY and 2D-NOESY pectra were successfully acquired: COSY cross peaks were observed in the only 1.0-4.5 ppm, however, NOESY cross peaks were observed in the 1.0-4.5 ppm and 7.9 ppm. From the result of the 2-D COSY data, cross peaks between the methyl protons ($CH_3$(3)) at 1.33 ppm and methine proton (CH(2)) at 4.11 ppm were observed in Lac. Cross peaks between the methylene protons (CH2(3,$H{\alpha}$)) at 2.50ppm and methylene protons ($CH_2$,(3,$H_B$)) at 2.70 ppm were observed in NAA. Cross peaks between the methine proton (CH(5)) at 3.27 ppm and the methine proton (CH(4,6)) at 3.59 ppm, between the methine proton (CH(1,3)) at 3.53 ppm and methine proton (CH(4,6)) at 3.59 ppm, and between the methine proton (CH(1,3)) at 3.53 ppm and methine proton (CH(2)) at 4.05 ppm were observed in Ins. From the result of 2-D NOESY data, cross peaks between the NH proton at 8.00 ppm and methyl protons ($CH_3$) were observed in NAA. Cross peaks between the methyl protons ($CH_3$(3)) at 1.33 ppm and methine proton (CH(2)) at 4.11 ppm were observed in Lac. Cross peaks between the methyl protons (CH3) at 3.03 ppm and methylene protons (CH2) at 3.93 ppm were observed in Cr. Cross peaks between the methylene protons ($CH_2$(3)) at 2.11 ppm and methylene protons ($CH_2$(4)) at 2.35 ppm, and between the methylene protons($CH_2$ (3)) at 2.11 ppm and methine proton (CH(2)) at 3.76 ppm were observed in Glu. Cross peaks between the methylene protons (CH2 (3)) at 2.14 ppm and methine proton (CH(2)) at 3.79 ppm were observed in Gln. Cross peaks between the methine proton (CH(5)) at 3.27 ppm and the methine proton (CH(4,6)) at 3.59 ppm, and between the methine proton (CH(1,3)) at 3.53 ppm and methine proton (CH(2)) at 4.05 ppm were observed in Ins. Conclusion : The present study demonstrated that in vitro 2D-COSY and NOESY represented the 3-bond and spatial connectivity of human brain metabolites by scalar coupling and dipolar NOE interaction. This study could aid in better understanding the interactions between human brain metabolites in vivo 2DCOSY study.

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A Gas Phaes Kinetic Study of the Energy Transfer by using the High Power CO$_2$ Laser. (II). Decomposition of $BrCH_2CH_2CH_2CH_2Cl$

  • Lee, Yong-Sik;Kim, Yang-Sik;Jeoung, Sae-Chae;Choo, Kwang-Yul
    • Bulletin of the Korean Chemical Society
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    • v.9 no.3
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    • pp.161-164
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    • 1988
  • Infrared multiphoton decompositions (IRMPD) of $BrCH_2CH_2CH_2CH_2Cl$ were studied by using the pulsed $CO_2$laser. At 0.3 J laser energy the experimentally observed product ratios could be reasonably explained by the RRKM calculation with initial excitation energy of ca. 80 Kcal/mol. The pressure dependence of product yields led us to conclude that the collisional deactivation by the inert gas decreased the yield of low energy dissociation channel more significantly.