• 제목/요약/키워드: Cations

검색결과 1,338건 처리시간 0.036초

Comparing the Stability of Geometrically rigid Tricyclopropyl Carbinyl Cations by $^{19}$F NMR Spectroscopy

  • Shin, Jung-Hyu;Kim, Kyong-Tae;Shin, Hun-Woo
    • Bulletin of the Korean Chemical Society
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    • 제8권3호
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    • pp.144-145
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    • 1987
  • The relative stability as function of geometry in the rigid tricyclopropylcarbinyl cations with varied bond angle (${\alpha}$) between the plane of cyclopropane ring and the bond connecting cyclopropane ring to cationic carbon was examined by $^{19}F$ nmr spectroscopy. 7-p-Fluorophenyltricyclo[2.2.2.$0^{2,6}$]octan-7-yl(4) and 8-p-fluorophenyltricyclo[3.2.2.$0^{2,7}$]nonan-8-yl cation (8) were generated from corresponding tertiary alcohols under stable ion conditions, and their $^{19}F$ chemical shifts were compared with those of model compounds such as 7-nortricyclyl cation (3) and tricyclo[3.3.1.$0^{2,7}$]octan-8-yl cation (7). Consequently, it is concluded that the varied orientation of bond angle (${\alpha}$) within in the bisected conformation does not affect degree of the charge delocalization into cyclopropane ring.

Solvent Effects on Localized and Delocalized Cationic Charges in Solvolysis$^1$

  • 이익준;고한중;장병두
    • Bulletin of the Korean Chemical Society
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    • 제16권11호
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    • pp.1104-1108
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    • 1995
  • A measure of stabilities (-ΔHo) and resonance delocalization (-Δq(Cα+)) for some carbocations has been estimated using the semiempirical AM1 method. The stability (-ΔHo) of carbocations can be correlated with the sensitivity (m) of localized cations to the solvent ionizing power scale Y, whereas the extent of resonance delocalization (-Δq(Cα+)) can be correlated with the sensitivity (h) of delocalized cations to the solvent ionizing power scale Ⅰ. It has been shown that two solvent ionizing power scales Y and I have in general opposite signs so that effects of electrostatic solvation are opposite for the localized and delocalized cationic charges. The use of two different solvent scales for a substrate with delocalizable cationic charge is not only prerequisite to the proper correlation of solvolysis rates but also is justified.

Lead-selective PVC Membrane Electordes Based on Bis(Crown ether)s

  • 오금철;강은철;정규성;팽기정
    • Bulletin of the Korean Chemical Society
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    • 제20권5호
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    • pp.556-558
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    • 1999
  • Lead-selective PVC membrane electrodes based on newly synthesized bis(crown ether)s containing 18-crown-6 moiety was prepared using standard PVC membrane composition. In order to monitor lead in environmental samples by lead sensor, especially good selectivity over alkali and alkaline earth metals has to be obtained. Thus, responses of the PVC membrane prepared with new bis(crown ether)s and Fluka ionophore V (crown ether) base to various cations include lead, alkali and alkaline earth metal ions were investigated for their use as a lead sensor. The polymeric liquid membrane based on trans-1 8-crown-6 ether exhibits the best overall potentiometric performances as a lead-selective electrode in terms of a wide linear dynamic range (between 10-6 and 10-2 M, Pb2+), excellent detection limit (less than 10-6 M) and good durability within limited error. The preferences of lead over other cations, such as Ag+, Hg2+, Na+, Ca2+ and even K+ in the aforementioned electrode are much better than the Fluka ionophore V system.

Potentiometric Characteristics of Ion-Selective Electrodes Based on Upper-Rim Calix[4]crown Neutral Carrier

  • 강유라;오현준;이경문;차근식;남학현;백경수;임혜재
    • Bulletin of the Korean Chemical Society
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    • 제19권2호
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    • pp.207-211
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    • 1998
  • Potentiometric characteristics of DOS plasticized PVC-based membranes containing upper-rim calix[4]crown neutral carrier to various metal cations and protonated alkylamines have been examined. Although the calix[4]crown-based membrane electrodes exhibited substantial emf responses to alkali and alkaline earth metal cations, their high detection limits (- log[Cs+]=4.5) and sub-Nernstian response slopes (48 mV/pCs+) to the most selective cation, cesium, indicate that the metal cation complexing ability of calix[4]crown is much weaker than that of macrocyclic crown ethers. However, the calix[4]crown-based membrane electrodes exhibited near-Nernstian response slopes (56 mV/decade for hexylNH3+) with low detection limits (log[hexylNH3+]= - 6.7) to most alkylammonium ions compared to those of blank (DOS plasticized PVC membrane with no ionophore) or crown ether-based membranes. While the selectivity patterns of blank and crown ether-based membranes are determined primarily by the lipophilicity of alkylammonium ions, the membranes doped with calix[4]crown ionophore could effectively discriminate the steric shapes of nonpolar alkyl groups of alkylammonium ions.

Theoretical Studies on the Base-Catalyzed Deprotonation of Sulfonyl-Activatec Carbon Acids

  • 김왕기;류완선;손창국;이본수;김창곤;이익준
    • Bulletin of the Korean Chemical Society
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    • 제18권2호
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    • pp.208-212
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    • 1997
  • Theoretical AM1 MO studies are reported on the gas-phase deprotonations of N-methyl 4-((Y-phenylsulfonyl)pyridinium cations (Ⅳ) and N-(Y-benzyl) 4-((phenylsulfonyl)methyl pyridinium cations (Ⅴ) using NH3 as a base. Bronsted α values for deprotonation of Ⅳ and Ⅴ are 0.18 and 0.17, respectively. Bronsted β value of 0.53 is found for the deprotonation of Ⅳ and Ⅴ by substituted aniline bases. The negative transition state (TS) imbalances, Ⅰ(=α-β) < 0, are rationalized by the negative distance factor, Δd (=dp-dTS) < 0, where dp and dTS are the distance between anionic charge center and substituents in the product and in the TS, respectively. The inability of d-pπ-conjugation in Ⅳ, where instead n-σ* type sigma delocalization occurs, causes very little lag in the structural reorganization in the TS.

Strong Absorption of Cations into a Cation Exchange Resin in Concentrated HClO$_4$

  • 김선호;김성수;김강진
    • Bulletin of the Korean Chemical Society
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    • 제6권4호
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    • pp.225-228
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    • 1985
  • The absorptions of Fe(Ⅲ), Tb(Ⅲ), Tl(Ⅰ), Ce(Ⅲ), Th(Ⅳ), and $UO_2^{2+}$ ions into the Dowex 50W-X2, 100-200 mesh resin were investigated by spectrophotometry to understand the abnormal strong absorption behavior of cations to cation exchange resins in concentrated HClO4. The distribution coefficients increase in the order : Tl(Ⅰ) < Fe(Ⅲ) < Tb(Ⅲ)∼Ce(Ⅲ) < $UO_2^{2+}$< Th(Ⅳ) and the order is interpreted in terms of the ratio of charge-to-ionic radius. The mole ratios of increment of $ClO_4^-$ ion absorption to metal ion absorption showed the same order as the distribution coefficients, which indicates that the electrostatic association between $ClO_4^-$ ion and metal ion plays a major role in the strong absorption.

Modulation of electroosmosis using penetration enhancers

  • Kim, Su-Youn;Lee, Yeon-Joo;Lee, Hyung-Won;Lee, Hyo-Jung;Lee, Seung-Yeon;Youe, Jee-Sun;Oh, Seaung-Youl
    • 대한약학회:학술대회논문집
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    • 대한약학회 2003년도 Proceedings of the Convention of the Pharmaceutical Society of Korea Vol.1
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    • pp.293.1-293.1
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    • 2003
  • Electroosmotic flux during iontophoresis originates due to the net negative charge of the current passing channels (pores) in skin at physiological pH (pH 7.4). Thus, the channels are permselective to cations, and this causes the convective solvent flow from anode to cathodal direction. This solvent flow facilitates the flux of cations (from anode), inhibits that of anions (from cathode), and enables theenhanced transport of neutral, polar solutes. (omitted)

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Effect of Polyethlene Glycols on the Electroosmosis Through Skin

  • Lee, Seung-Yeon;Kim, Su-Youn;Youe, Jee-Sun;Min, Hye-Ran;Han, Jeong-Jin;Oh, Seaung-Youl
    • 대한약학회:학술대회논문집
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    • 대한약학회 2003년도 Proceedings of the Convention of the Pharmaceutical Society of Korea Vol.2-2
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    • pp.233.3-234
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    • 2003
  • Electroosmotic flux during iontophoresis originates due to the net negative charge of the current passing channel (pores) in skin at physiological pH (pH 7.4). Thus, the channel is permselective to cations, and this causes the convective solvent flow, from anode to cathode direction. This solvent flow facilitates the flux of cations (from anode), inhibits that of anions (from cathode), and enables the enhanced transport of neutral, polar solutes. In this work, we have investigated the effect of a series of polyethylene glycols (PEGs) with different molecular weights on the electroosmtic flow to get more detail understanding of this phenomena. (omitted)

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Adsorption Behaviors for Strontium and Cesium Ions Using Composite Ion Exchangers

  • Kim, H.T.;Han, H.S.;Shul, Y.G.;Moon, J.K.;Oh, W.Z.;Lee, E.H.
    • 한국방사성폐기물학회:학술대회논문집
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    • 한국방사성폐기물학회 2004년도 Proceedings of the 4th Korea-China Joint Workshop on Nuclear Waste Management
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    • pp.1-11
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    • 2004
  • PAN-4A composite ion exchanger was more selective for Sr ion than other cations and PAN-KCoFC composite ion exchanger has much higher ion exchange capacity for Cs ion than other cations. The ion exchange capacities obtained from Dubinin-Polanyi equation were 3.93 meq/g for Sr ion and 1.50 meq/g for Cs ion using PAN-4A and PAN-KCoFC ion exchangers, respectively. The modified Dubinin-Polanyi model fit the experimental data accurately in multi-component system. The effective surface diffusivities $(D_{s, cff})$ for Sr and Cs ions of PAN-4A and PAN-KCoFC ion exchangers were slightly increased with the different particle sizes.

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