• Title/Summary/Keyword: Substitution reaction

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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.

Determination of Stereochemistry of Acetoxy 1,3-Oxathiolane (아세톡시 1,3-옥사티올란의 입체화학의 결정)

  • Hahn, Hoh Gyu;Chang, Kee Hyuk;Lee, Wha Suk;Ma, He Duck
    • Journal of the Korean Chemical Society
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    • v.40 no.5
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    • pp.357-364
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    • 1996
  • Stereochemistries of acetoxy 1,3-oxathiolane 1 were determined by two methods. First, the structures of $\alpha$ isomer 7 and $\beta$ isomer 9 were confirmed by the difference of their conversion rates to dihydrooxathiin 2 under acid catalysis. When the acetoxy leaving group is located in trans relationship to sulfur, a isomer in which carboxanilide is less hindered sterically against the 1,3-oxathiolane ring is $\beta$ isomer 7, and the other isomer of which the reaction rate is slower than 7 is $\beta$ isomer 9. Second, in the deuterium reactions of diastereomeric sulfoxides, the isomers of which methine hydrogen is substituted to deuterium were cis isomers 15 and 17, and another isomers of which methyl hydrogen is substituted to deuterium were trans isomers 16 and 18. Substitution of either methine or methyl hydrogen to deuterium resulted from stereospecific ring opening followed by recyclization by [2,3] sigmatropic rearrangement.

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The crystal growth and the electrochemical property of $LiZn_xMn{2-x}O_4(0\leqq x \leqq$ 0.15) cathode material ($LiZn_xMn{2-x}O_4(0\leqq x \leqq$ 0.15) 정극 활물질의 결정 성장 변화와 전기 화학적 특성)

  • Jeong, In-Seong;Gu, Hal-Bon;Lee, Jin;Park, Gye-Choon
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 1999.05a
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    • pp.133-136
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    • 1999
  • We report on the electrochemical properly of LiZ $n_{x}$Mn $_{2-x}$ $O_4$ for different degrees of Zn substitution(x) Though all cathode material showed spinel phase based on cubic phase in X-ray diffraction, other peaks(M $n_2$ $O_3$ or M $n_3$ $O_4$) gradually exhibited and became intense with the increase of x vague in LiZ $n_{x}$Mn $_{2-x}$ $O_4$. In addtion, TG-DTA analysis exhibited that both LiM $n_2$ $O_4$ and LiZ $n_{0.1}$ M $n_{1.9}$ $O_4$ occurred the weight loss(TG) and the endothermic and exothermic reaction(DTA) until 80$0^{\circ}C$ When x=0.1 in LiZ $n_{x}$Mn $_{2-x}$ $O_4$ cathode materials showed the charge and discharge capacity of about 100mAh/g at first cycle and about 70mAh/g after tooth cycle.cle.e.cle.e.e.e.

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Effect of Ti substitution on electrochemical properties $Li_{0.44}MnO_2$ synthesized by solid state reaction (고상반응법에 의해 제조된 $Li_{0.44}MnO_2$의 전기화학적 성질에 미치는 Ti 치환의 영향)

  • ;Marca M. Doeff;Abraham Anapolsky;Thomas J. Richardson
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.10 no.5
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    • pp.362-366
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    • 2000
  • $Li_{0.44}MnO_2$cathode material has high reversibility during lithium insertion processes and is not easily damaged through over-charging or over-discharging. $Mn_2O_3$is often present as an impurity phase, and reduce the electrochemical capacity of electrode because this phase is electrochemically inert. Adding of excess NaOH reduced the $Mn_2O_3$to the content under undetectable by X-ray diffraction. Because the capacity can be increased in the cathode materials with larger unit cell, some of the manganese was replaced with titanium having larger ion size, and powders with the formula $Li_{0.44}T_{iy}Mn_{1-y}O_2$(where y = 0.11, 0.22, 0.33, 0.44, and 0.55) was synthesized and characterized. A maximum reversible capacity of 150 mAh/g was obtained for $Li/P(EO)_8$LiTFSI/$Li_{0.44}Ti_{0.22}Mn_{0.78}O_2$cells in electrochemical potential spectroscopy (ECPS) experiments. Cells with the titanium-doped manganese oxides exhibited a fade rate of 0.12 % or less per cycle.

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Metal-Ion Catalysis in Alkaline Ethanolysis of 2-Pyridyl Thionobenzoate: Effects of Modification of Electrophilic Center from C=O to C=S

  • Um, Ik-Hwan;Song, Yoon-Ju;Kim, Min-Young;Lee, Jae-In
    • Bulletin of the Korean Chemical Society
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    • v.34 no.5
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    • pp.1525-1529
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    • 2013
  • Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the nucleophilic substitution reactions of 2-pyridyl thionobenzoate (5b) with alkali-metal ethoxides (EtOM, $M^+=Li^+$, $Na^+$, $K^+$, and 18-crown-6-ether complexed $K^+$) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. $[EtOM]_o$ curve upward regardless of the nature of the $M^+$ ions, while those of $k_{obsd}/[EtO^-]_{eq}$ vs. $[EtO^-]_{eq}$ are linear with a positive intercept. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the ion-paired EtOM is more reactive than the dissociated $EtO^-$, and $M^+$ ions catalyze the reactions in the order $K^+$ < $Na^+$ < $Li^+$ < 18C6-complexed $K^+$. The plot of log $k_{EtOM}$ vs. $1/r_{Stokes}$ results in an excellent linear correlation, indicating that the reactions are catalyzed by the solvated $M^+$ ions but not by the bare $M^+$ ions. The reactions of 5b with EtOM have been concluded to proceed through a six-membered cyclic TS, in which the solvated $M^+$ ions increase the electrophilicity of the reaction center and the nucleofugality of the leaving group.

Effects of Partial Substitution of CeO2 with M2O3 (M = Yb, Gd, Sm) on Electrical Degradation of Sc2O3 and CeO2 Co-doped ZrO2

  • Shin, Hyeong Cheol;Yu, Ji Haeng;Lim, Kyoung Tae;Lee, Hee Lak;Baik, Kyeong Ho
    • Journal of the Korean Ceramic Society
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    • v.53 no.5
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    • pp.500-505
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    • 2016
  • Scandia-stabilized zirconia co-doped with $CeO_2$ is a promising electrolyte for intermediate temperature SOFC, but still shows rapid degradation during a long-term operation. In this study, $CeO_2$ (1 mol%) as a stabilizer is partially substituted with lanthanum oxides ($M_2O_3$, M=Yb, Gd, Sm) to stabilize a cubic phase and thus durability in reducing atmosphere. 0.5M0.5Ce10ScSZ electrolytes were prepared by solid state reaction and sintered at $1450^{\circ}C$ for 10 h to produce dense ceramic specimens. With addition of the lanthanum oxide, 0.5M0.5Ce10ScSZ showed lower degradation rates than 1Ce10ScSZ. Since $Gd_2O_3$ showed the highest ionic conductivity among the co-dopants, an electrolyte-supported cell with 0.5Gd0.5Ce10ScSZ was prepared to compare its long-term performance with that of 1Ce10ScSZ-based cell. Maximum power density of 0.5Gd0.5Ce10ScSZ-based cell was degraded by about 2.3% after 250 h, which was much lower than 1Ce10ScSZ-based cell (4.2%).

Adsorption of Uranium(VI) Ion Utilizing Cryptand Ion Exchange Resin (Cryptand 이온교환 수지를 이용한 우라늄(VI) 이온의 흡착)

  • Park, Seong-Kyu;Kim, Joon-Tae
    • Analytical Science and Technology
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    • v.17 no.2
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    • pp.91-97
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    • 2004
  • Cryptand ion exchange resins were synthesized with 1-aza-15-crown-5 macrocyclic ligand attached to styrene divinylbenzene (DVB) copolymer with crosslink of 1%, 2%, 5% and 10% by substitution reaction. The synthesis of these resins was confirmed by content of chlorine, element analysis, and IR-spectrum. The effects of pH, time, dielectric constant of solvent and crosslink on adsorption of uranium ($UO{_2}^{2+}$) ion were investigated. The uranium ion was showed fast adsorption on the resins above pH 3. The optimum equilibrium time for adsorption of metallic ions was about two hours. The adsorption selectivity determined in ethanol was in increasing order uranium ($UO{_2}^{2+}$), magnesium ($Mg^{2+}$), neodymium ($Nd^{3+}$) ion. The adsorption was in order of 1%, 2%, 5%, and 10% crosslink resin and adsorption of resin decreased in proportion to order of dielectric constant of solvents.

Modulation of Inwardly Rectifying $K^+$ Channel by Intracellular and Extracellular pH in Bovine Aortic Endothelial Cells

  • Park, Kyu-Sang;Kong, In-Deok;Lee, Joong-Woo;Rhim, Hye-Whon;Kim, Young-Chul;So, In-Suk;Kim, Ki-Whan
    • The Korean Journal of Physiology and Pharmacology
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    • v.6 no.5
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    • pp.255-260
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    • 2002
  • The effects of intracellular and extracellular pH on the inwardly rectifying $K^+$ (IRK) channel of the bovine aortic endothelial cells (BAECs) were examined using whole-cell patch-clamp technique. The IRK current, efficiently blocked by $Ba^{2+}\;(200{\mu}M),$ is the most prominent membrane current in BAECs, which mainly determines the resting membrane potential. The expression of Kir2.1 was observed in BAECs using reverse transcriptase-polymerase chain reaction (RT-PCR) analysis. Intracellular alkalinization, elicited by the extracellular substitution of NaCl with $NH_4Cl$ (30 mM), significantly augmented the amplitude of IRK current. On the contrary, the amplitude of IRK current was attenuated by the Na-acetate (30 mM)-induced intracellular acidification. The changes in extracellular pH also closely modulated the amplitude of IRK current, which was decreased to $40.2{\pm}1.3%$ of control upon switching the extracellular pH to 4.0 from 7.4. The extracellular pH value for half-maximal inhibition (pK) of IRK current was 5.11. These results demonstrate that the activity of IRK channel in BAECs, probably Kir2.1, was suppressed by proton at both sides of plasma membrane.

The retrogradation and swelling power of modified potato starches (변성 감자 전분의 노화와 팽윤력)

  • Kim, Ji-Tae;Noh, Wan-Seob
    • Applied Biological Chemistry
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    • v.35 no.5
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    • pp.404-409
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    • 1992
  • Hydroxypropylated starches and acetylated starches were prepared by reaction of potato starch with propylene oxide and acetic anhydride, respectively and then degree of retrogradation and swelling power were investigated in different pHs and temperature. The extent of retrogradation determined by glucoamylase method during freeze-thaw treatment and storage in low temperature $(0{\sim}5^{\circ}C)$ showed that modified potato starches were slowly retrograded as the increase of degree of substitution. The order of the retrogradation tendencies in different pHs were pH 4>pH 6>pH 8>pH 10. Retrogradation of hydroxypropylated potato starches were less than that of acetylated potato starches. Swelling power of starches were influenced more by the temperature than by the pH. The order of the swelling power tendencies in different pHs were pH 10>pH 2>pH 8>pH 4>pH 6.

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Adsorption of Uranium (VI) Ion on the 1-Aza-12-Crown-4-Styrene-DVB Synthetic Resin Adsorbent (1-Aza-12-Crown-4-Styrene-DVB 합성수지 흡착제에 의한 우라늄(VI) 이온의 흡착)

  • Kim, Joon-Tae
    • Applied Chemistry for Engineering
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    • v.19 no.3
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    • pp.304-309
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    • 2008
  • Cryptand series ion exchange resins were synthesized with 1-aza-12-crown-4 macrocyclic ligand attached to styrene (4 series dangerous matter) divinylbenzene (DVB) copolymer with crosslink of 1%, 2%, 4% and 8% by a substitution reaction. The synthesis of these resins was confirmed by content of chlorine, element analysis, electron micrograph, and IR-spectrum. The effects of pH, time, dielectric constant of solvent and crosslink on adsorption of uranium (${UO_2}^{2+}$) ion were investigated. The uranium ion showed a fast adsorption on the resins above pH 3. The optimum equilibrium time for adsorption of metallic ions was about two hours. The adsorption selectivity determined in ethanol was in increasing order uranium (${UO_2}^{2+}$) > nickel ($Ni^{2+}$) > gadolinium ($Gd^{3+}$) ion. The adsorption was in order of 1%, 2%, 4%, and 8% crosslinked resin and adsorption of resin decreased in proportion to order of dielectric constant of solvents.