• Bulletin of the Korean Chemical Society
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• v.8 no.3
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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.

• Bulletin of the Korean Chemical Society
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• v.16 no.11
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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.

• Bulletin of the Korean Chemical Society
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• v.20 no.5
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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.

• Bulletin of the Korean Chemical Society
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• v.19 no.2
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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.

• Bulletin of the Korean Chemical Society
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• v.18 no.2
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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.

• Bulletin of the Korean Chemical Society
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• v.6 no.4
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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.

• Proceedings of the PSK Conference
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• 2003.04a
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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)

• Proceedings of the PSK Conference
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• 2003.10b
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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)

• Proceedings of the Korean Radioactive Waste Society Conference
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• 2004.02a
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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.

• Proceedings of the Zoological Society Korea Conference
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• 1998.10b
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• pp.288.2-288
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• 1998

No Abstract, See Full Text