• Title/Summary/Keyword: $CH_2Cl_2$

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Synthesis and Characterization of Tetrathiafulvalene (TTF) and 7,7,8,8-Tetracyanoquinodimethane (TCNQ) Compounds with PdX2(X=CI, NO3and Hexafluoroacetylacetonate)

  • Kim, Young-Inn;Jeong, Chan-Kyou;Lee, Yong-Min;Choi, Sung-Nak
    • Bulletin of the Korean Chemical Society
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    • v.23 no.12
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    • pp.1754-1758
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    • 2002
  • Tetrathiafulvalene(TTF) reacts with $PdCl_2,Pd(NO_3)_2$ and $Pd(hfacac)_2$(hexafluoroacetylacetonate) in ethanol to give $(TTF)_{1.5}PdCl_2$ (1a), $(TTF)_3Pd(NO_3)_2$ (1b) and $(TTF)_4Pd(hfacas)_2$ nd (1c), respectively. $PdCl(TCNQ)_{2.5}{\cdot}CH_3OH(2a)$was obtained from the reaction of $PdCl_2$ with LiTCNQ in methanol via the partial replacement of $Cl^-$ in $PdCl_2$ by $TCNQ^-$anion, whereas the total substitution of the labile $NO_3^-$ in $Pd(NO_3)_2$ yielded pd(TCNQ)·$CH_3OH$ (2b). $Pd(hfacac)_2(TCNQ)_2\cdot3CH_3OH$ (2c) was obtained from $Pd(hfacac)_2$ and LiTCNQ in methanol. The prepared compounds were characterized by spectroscopic (IR, UV, XPS) methods and magnetic (EPR, magnetic susceptibility) studies. The powdered electrical conductivities (${\sigma}_{rt}$) of the prepared compounds at room temperature were about~$10^{-7}S{\cdot}cm^{-1}$. The effective magnetic moments were lass than the spin-only value of one unpaired electron and no EPR signals from Pd metal ions were observed in any of the compounds, indicating that the Pd ions were diamagnetic and the magnetic moments arose from$(TTF)_n$ or $(TCNQ)_n$ moieties. The experimental evidences revealed that the charge transfer had occurred form $(TTF)_n$ moiety to the central Pd metal ion in 1a, 1b and 1c. Thus the TTF donors were ions in 2a and 2b were diamagnetic Pd(II) oxidation state. In contrast, the Pd metal ion was oxidized to Pd(IV) state in 2c as a result of an addition of $TCNQ^-$anion to $Pd(hfacac)_2$ in methanol. The oxidation states of the Pd metal ions were confirmed using the x-ray photoelectron spectroscopy.

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.

Structural characteristics of [N(CH3)4]2CdCl4 determined by 1H MAS NMR, 13C CP/ MAS NMR, and 14N NMR

  • Lee, Seung Jin;Lim, Ae Ran
    • Journal of the Korean Magnetic Resonance Society
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    • v.19 no.1
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    • pp.18-22
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    • 2015
  • The structural geometry of $[N(CH_3)_4]_2CdCl_4$ in a hexagonal phase is studied by $^1H$ MAS NMR, $^{13}C$ CP/MAS NMR, and $^{14}N$ NMR. The changes in the chemical shifts for $^{13}C$ and $^{14}N$ in the hexagonal phase are explained by the structural geometry. In addition, the temperature dependencies of the spin-lattice relaxation time in the rotating frame $T_{1{\rho}}$ for $^1H$ MAS NMR and $^{13}C$ CP/MAS NMR are measured.

Inhibitory Effects of Carex pumila Extracts on MMP-2 and MMP-9 Activities in HT-1080 Cells (HT-1080 세포주에서 좀보리사초 추출물의 MMP-2와 MMP-9 활성 억제효과)

  • Kim, Junse;Kong, Chang-Suk;Seo, Youngwan
    • Ocean and Polar Research
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    • v.40 no.4
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    • pp.249-257
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    • 2018
  • Matrix metalloproteinases (MMPs) are associated with the invasion and metastasis of malignant tumors composed of cancer cells in an increased state of expression. This study evaluates the inhibitory effect of Carex pumila on MMP-2 and MMP-9 activity in phorbol-12-myristate-13-acetate (PMA)-stimulated HT-1080 human fibrosarcoma cells using gelatin zymography, MMPs enzyme-linked immunosorbent assay (ELISA), reverse transcription-polymerase chain reaction (RT-PCR) and Western blot assay. C. pumila was extracted twice with dichloromethane ($CH_2Cl_2$) and methanol (MeOH). Treatment with $CH_2Cl_2$ extract and MeOH extract in PMA-stimulated HT-1080 cells effectively reduced the production of MMP-2 and 9. Also, the combined crude extracts ($CH_2Cl_2$ and MeOH) significantly inhibited the enzymatic activities and the expression of MMP-2 and MMP-9 in mRNA and protein levels. The combined crude extracts were partitioned between $CH_2Cl_2$ and water. The organic layer was further fractionated with n-hexane, 85% aqueous methanol (85% aq.MeOH) and the aqueous layer was separated into n-butanol and water, successively. Of the fractions, 85% aq.MeOH fraction showed the highest inhibitory activity of MMP-2 and MMP-9 in gelatin zymography and MMP ELISA kit. Furthermore, 85% aq.MeOH fraction most significantly suppressed cell migration. In RT-PCR and Western blot assay, n-butanol and 85% aq.MeOH fractions exerted the greatest inhibition on mRNA and protein expression of MMP-2 and MMP-9, respectively. As a result, C. pumila can be used as a good anti-invasive agent source.

The Chemical Constituents of the Stem Barks of Fraxinus rhynchophylla (물푸레나무(Fraxinus rhynchophylla) 수피의 추출성분)

  • Yang, Eun-Ju;Lee, Dong-Geun;Lee, Jong-Won;Kim, Yae-Sil;Lim, Sun-Ha;Song, Kyung-Sik
    • Applied Biological Chemistry
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    • v.50 no.4
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    • pp.348-351
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    • 2007
  • The stem barks of Fraxinus rhynchophylla was extracted with 95% EtOH, and the concentrated extract was successively partitioned with $CH_2Cl_2$, n-BuOH, and $H_2O$ in order to investigate the major phytochemicals. From the $CH_2Cl_2$ soluble fraction, a sterol (1) was isolated through the repeated silica gel column chromatographies. Three additional compounds (2-4) were isolated from the n-BuOH soluble fraction through silica gel, RP-18, and Sephadex LH-20 column chromatographies. Their chemical structures were elucidated as daucosterol $(1;{\beta}-sitosterol-3-O-{\beta}-D-glucopyranoside)$, caffeic acid (2), 6,8-dihydroxy-7-methoxycoumarin (3), and coniferaldehyde glucoside (4) by comparing their spectral data with those in the literatures. All isolates (1-4) were the first to be isolated from F. rhynchophylla.

Convolutive Cyclic Voltammetry Investigation of Dicarboximide Laser Dye at a Platinum Electrode in 1,2-Dichloroethane (1,2-Dichloroethane 내 백금 전극에서의 dicarboximide 레이저 염료에 대한 convolutive 순환 전압-전류법 연구)

  • Al-Bishri, Hassan M.;El-Mossalamy, E.H.;El-Hallag, Ibrahim;El-Daly, Samy
    • Journal of the Korean Chemical Society
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    • v.55 no.2
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    • pp.169-176
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    • 2011
  • The electrochemical investigation of N,N-bis (2,5-di-tert-butylphenyl)-3,4,9,10 perylenebis (dicarboximide) laser dye have been carried out using cyclic voltammetry and convolution - deconvolution voltammetry combined with digital simulation technique at a platinum electrode in 0.1 mol/L tetrabutyl ammonium perchlorate (TBAP) in solvent 1,2 dichloroethane ($CH_2Cl-CH_2Cl$). The investigated dye was reduced via consumption of two sequential electrons to form radical anion and dianion (EE mechanism). In switching the potential to positive scan, the compound was oxidized by loss of two electrons, which were followed by a fast aggregation process ($EC_1EC_2$ mechanism). The electrode reaction pathway and the chemical and electrochemical parameters of the investigated compound were determined using cyclic voltammetry and convolutive voltammetry. The extracted electrochemical parameters were verified and confirmed via digital simulation method.

The Effects of Charge Transfer Complex on the Reaction of Aniline and Iodine (Aniline과 Iodine간의 반응에 있어서 전하이동 착물의 영향)

  • Oh-Yun Kwon;U-Hyon Paek;Eung-Ryul Kim
    • Journal of the Korean Chemical Society
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    • v.36 no.2
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    • pp.174-179
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    • 1992
  • Reaction of aniline and iodine in$CHCl_3,\;CH_2Cl_2 : CHCl_3$(1 : 1), and $CH_2Cl_2$ has been studied kinetically by using conductivity method, Pseudo first-order rate constants ($k_{obs}$) and second-order rate constants ($k_{obs}$/[aniline]) are dependent on the aniline concentration. Second-order rate constants obtained were increased with increasing aniline concentration. We analysed these results on the basis of formation of charge transfer complex as reaction intermediate. From the construction of react ion scheme and derivation of rate equation, we calculated equilibrium constants and activation parameters for the formation and transformation of charge transfer complex. The equilibrium constants were decreased by an increase in the dielectric constant of the solvent and the value is 1.7-3.7$M^{-1}$. The rate of transformation are markedly affected by the solvent polarity. ${\Delta}H^{\neq}$ is about 14.2kJ/mol, and ${\Delta}S^{\neq}$ is large negative value of -243J/mol K.

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Reaction of Potassium Fluoride with Organic Halogen Compounds. (Part I) Reactions of Potassium Fluoride with Organic Halides, Acids, and Esters in presence of Dimethyl Formamide and their Pyrolytic Decaboxylation in presence of Potassium Fluoride (有機 할로겐 化合物과 弗化加里의 反應 (第1報) 有機 할라이드, 酸 및 에스테르와 弗化加里의 디메칠 호름아마이드 溶媒系反應 및 高溫-脫炭酸-熱分解反應)

  • You Sun Kim
    • Journal of the Korean Chemical Society
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    • v.7 no.3
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    • pp.189-196
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    • 1963
  • Reactions between potassium fluoride with organic halogen-containing carboxylic acids in dimethyl formamide solvent gave a decarboxylation reaction for the case of fluoro carboxylic acids of the type of $CF_3\;COOH,\;C_3F_7COOH,\;and\;C_2F_5COOH,$ whereas an additional partial fluorination together with dimerization reaction occurred for the chlorine containing acids of the type of $CH_2ClCOOH,\;CH_3CHClCOOH, \;CHCl_2COOH\;and\;o-Cl-C_6H_4-COOH.$ The phenyl halides showed no reactivity, but the halides with two electron attracting substituents on the benzene ring gave mainly dimerization reaction. The esters and alcohols gave an usual fluorination reaction. The same reactions in absence of the solvent at the elevated temperature increase the yield of the dimerized product and gave the cyclized product, fluorenone, in case of ο-chlorobenzoic acid. It was found that the fluorination usually precede the decarboxylation reaction by checking the stiochemical sequence of reaction. Catalytic influence of potassium fluoride were discussed and the mechanism of the reaction was considered.

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