• Bulletin of the Korean Chemical Society
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• v.19 no.2
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• pp.147-150
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• 1998

• Bulletin of the Korean Chemical Society
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• v.2 no.3
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• pp.114-121
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• 1981

Reactions of thioxanthylium ion with dimethyl-, dibenzyl-, diisopropyl-, and diphenylmercury in the air gave 9,9'-methylenedithioxanthene, 9-benzylthioxanthene, 9-acetonylthioxanthene, and 9-phenylthioxanthene, respectively, as a 9-substituted thioxanthene. In contrast with reactions with aromatics with an electron-donating group, large amount of thioxanthene and thioxanthone were obtained. However, only trace amounts of thioxanthene and thioxanthone were obtained from the reaction with dibenzylmercury under nitrogen atmosphere. In order to explain these reactions, one electron transfer between thioxanthylium ion and organomercurials was proposed.

• Bulletin of the Korean Chemical Society
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• v.22 no.7
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• pp.669-672
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• 2001

Pseudo-first-order rate constants have been measured spectrophotometrically for the title reactions. The plot of kobs vs the concentration of alkali metal ethoxides is linear for the reactions performed in the presence of complexing age nt, 18-crown-6 ether, but curved upwardly for the corresponding reactions performed in the absence of the complexing agent, indicating that the alkali metal ions studied in this study behave as a catalyst. The catalytic effect was found to increase in the order Li+ << K+ ${\leq}$ Na+. Second-order rate constants were determined for the reactions with dissociated free ethoxide (kEtO-) and with ion paired alkali metal ethoxides (kEtO-M+ ) from ion pairing treatments. The magnitude of catalytic effect (kEtO-M+/kEtO-) was found to be 2.3, 9.5 and 8.7 for the reaction of 8-(5-nitroquinolyl) 2-furoate, while 1.4, 3.6 and 4.2 for that of 4-nitrophenyl 2-furoate, indicating that the catalytic effect is larger in the reaction of the former substrate than in that of the latter one. The larger catalytic effect was attributed to two possible complexing sites with alkali metal ions in the former substrate.

• Bulletin of the Korean Chemical Society
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• v.9 no.5
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• pp.298-303
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• 1988

Kinetic studies on cupric ion ($Cu^{2+}$) oxidation of 1-benzyl- and 1-aryl-1,4-dihydronicotinamides (XNAH) in aqueous solution were performed. In the presence of dioxygen ($O_2$), the reaction followed first order kinetics with respect to both XNAH and $Cu^{2+}$. The oxidation reaction was found to be independent and parallel to the acid-catalyzed hydration reaction of XNAH. The catalytic role of $Cu^{2+}$ for the oxidation of XNAH in the presence of $O_2$ was attributed to $Cu^{2+}/Cu^+$ redox cycle by the reactions with XNAH and $O_2$. The second order rate constants of the Cu2+ oxidation reaction kCu, and acid-catalyzed hydration reaction $k_H$ were strongly dependent on the nature of the substituents in 1-aryl moiety. The slopes of log $k_{Cu}$ vs log $K_H$ and log $k_{Cu}$ vs ${\sigma}_p$ of the substituents plots were 1.64 and -2.2, respectively. This revealed the greater sensitivity of the oxidation reaction rate to the electron density on the ring nitrogen than the hydration reaction rate. A concerted two-electron transfer route involving XNAH-$Cu^{2+}$ complex was proposed for mechanism of the oxidation reaction.

• Applied Chemistry for Engineering
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• v.24 no.5
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• pp.443-455
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• 2013

Electrochemical studies on charge transfer reactions across the interface between two immiscible electrolyte solutions (ITIES) have greatly attracted researcher's attentions due to their wide applicability in research fields such as ion sensing and biosensing, modeling of biomembranes, pharmacokinetics, phase-transfer catalysis, fuel generation and solar energy conversion. In particular, there have been extensive efforts made on developing sensing platforms for ionic species and biomolecules via gelifying one of the liquid phases to improve mechanical stability in addition to creating microscale interfaces to reduce ohmic loss. In this review, we will mainly discuss on the basic principles, applications and future aspects of various sensing platforms utilizing ion transfer reactions across the ITIES. The ITIES is classified into four types : (i) a conventional liquid/liquid interface, (ii) a micropipette supported liquid/liquid interface, (iii) a single microhole or an array of microholes supported liquid/ liquid interface on a thin polymer film, and (iv) a microhole array liquid/liquid interface on a silicon membrane. Research efforts on developing ion selective sensors for water pollutants as well as biomolecule sensors will be highlighted based on the use of direct and assisted ion transfer reactions across these different ITIES configurations.

• Journal of the Korean Chemical Society
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• v.28 no.2
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• pp.135-142
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• 1984

New type dioxygen bridged complexes of palladium were prepared by using $KO_2$ as a source of superoxide ion $(O_2^-)$. The method is completely different from the traditional one which has adopted the oxidative addition of molecular oxygen to transition metal complexes in low valency. It was suggested that the reaction to prepare the dioxygen complexes proceeded via nucleophilic displacement followed by electron transfer reaction. Five new type dioxygen complexes having ${\pi}$-allyl ligand were prepared and characterized by the application of the reaction of $O_2^-$.

• Applied Chemistry for Engineering
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• v.26 no.3
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• pp.372-376
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• 2015

6-MQCC (Cr(VI)-6-methylquinoline) complex was synthesized by the reaction of 6-methylquinoline with chromium(VI) trioxide in 6 M HCl. The structure was characterized using IR (Infrared Spectroscopy) and ICP (Inductively Coupled Plasma) analysis. The oxidation of benzyl alcohol using 6-MQCC in various solvents showed that the reactivity increased with the increase of the dielectric constant, in descending order of DMF > acetone > chloroform > cyclohexene. In the presence of DMF solvent with acidic catalyst such as sulfuric acid ($H_2SO_4$), 6-MQCC oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, $m-NO_2$) were effectively oxidized. Electron-donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. The Hammett reaction constant (${\rho}$) was -0.69 (308 K). The observed experimental data was used to rationalize the fact that the hydride ion transfer occurred at the rate-determining step.

• Applied Chemistry for Engineering
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• v.27 no.1
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• pp.110-114
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• 2016

Cr(VI)-pyrazine complex (PZCC) was synthesized by the reaction of pyrazine with chromium (VI) trioxide in 6 M HCl. The structure was characterized using IR spectroscopy and inductively coupled plasma (ICP). The oxidation of benzyl alcohol using PZCC in various solvents showed that the reactivity increased with the increase of the dielectric constant, in the order: N,N'-dimethylform-amide > acetone > chloroform > cyclohexene. In the presence of N,N'-dimethylformamide solvent with an acidic catalyst such as sulfuric acid ($H_2SO_4$ solution), PZCC oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, $m-NO_2$). Electron-donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. Hammett reaction constant (${\rho}$) was -0.70 (308 K). The observed experimental data were used to rationalize the hydride ion transfer in the rate-determining step.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.14 no.11
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• pp.6039-6046
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• 2013

Cr(VI)-heterocyclic complex[Cr(VI)-2-methylpyrazine] was synthesized by the reaction between of heterocyclic compound(2-methylpyrazine) and chromium trioxide, and characterized by IR and ICP analysis. The oxidation of benzyl alcohol using Cr(VI)-2-methylpyrazine in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order : cyclohexene${\rho}$) was Cr(VI)-2-methylpyrazine= -0.65(308K). The observed experimental data have been ratiolized. The hydride ion transfer causes the prior formation of a chromate ester in the rate-determining step.

• Applied Chemistry for Engineering
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• v.23 no.2
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• pp.241-246
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• 2012

Cr(VI)-heterocyclic complex (2,2'-bipyridinium dichromate) was synthesized by the reaction between of 2,2'-bipyridine and chromium trioxide in $H_2O$, and characterized by IR and ICP. The oxidation of benzyl alcohol using 2,2'-bipyridinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant, in the order: cyclohexene < chloroform < acetone < N,N-dimethylformamide. In the presence of DMF solvent with acidic catalyst such as $H_2SO_4$ solution, 2,2'-bipyridinium dichromate oxidized the benzyl alcohol and its derivatives (p-$p-OCH_3$, $m-CH_3$, H, $m-OCH_3$, m-Cl, $m-NO_2$). Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant was -0.66 (303 K). The observed experimental data was used to rationalize the hydride ion transfer in the rate-determining step.