• Bulletin of the Korean Chemical Society
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• 제32권spc8호
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• pp.3003-3008
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• 2011

Reactions of benzyl alcohol and its derivatives by [Ru$^{IV}$(tpy)(dcbpy)(O)]$^{2+}$ (tpy = 2,2':6',2"-terpyridine; dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) leading to the corresponding benzaldehydes in acetonitrile and water have been studied. Kinetic studies show that the reaction is first-order in both alcohol and oxidant, with k = 1.65 (${\pm}$ 0.1) $M^{-1}s^{-1}$ at $20^{\circ}C$, ${\Delta}H^{\ddag}$ = 4.3 (${\pm}$ 0.1) kcal/mol, ${\Delta}S^{\ddag}$ = -22 (${\pm}$ 1) eu, and $E_a$ = 4.9 (${\pm}$ 0.1) kcal/mol. High ${\alpha}$ C-H kinetic isotope effects are observed, but O-H solvent isotope effects are negligible. Spectral evidences with the isotope effects suggest that oxidation of benzyl alcohols occurs by a two-electron, hydride transfer. The catalytic cycles of aerobic benzyl alcohol oxidation are employed.

• 한국재료학회지
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• 제31권8호
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• pp.465-470
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• 2021

Deuterium is a crucial clean energy source required for nuclear fusion and is a future resource needed in various industries and scientific fields. However, it is not easy to enrich deuterium because the proportion of deuterium in the hydrogen mixture is scarce, at approximately 0.016 %. Furthermore, the physical and chemical properties of the hydrogen mixture and deuterium are very similar. Therefore, the efficient separation of deuterium from hydrogen mixtures is often a significant challenge when using modern separation technologies. Recently, to effectively separate deuterium, studies utilizing the 'Kinetic Quantum Sieving Effect (KQS)' of porous materials are increasing. Therefore, in this review, two different strategies have been discussed for improving KQS efficiency for hydrogen isotope separation performance using nanoporous materials. One is the gating effect, which precisely controls the aperture locally by adjusting the temperature and pressure. The second is the breathing phenomenon, utilizing the volume change of the structure from closed system to open system. It has been reported that efficient hydrogen isotope separation is possible using these two methods, and each of these effects is described in detail in this review. In addition, a specific-isotope responsive system (e.g., 2nd breathing effect in MIL-53) has recently been discovered and is described here as well.

• Bulletin of the Korean Chemical Society
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• 제20권5호
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• pp.573-576
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• 1999

The rate constants and kinetic solvent isotope effects (KSIE, KMeOH/kMeOD) for solvolyses of para-substituted phenylchloroformates in CH3OH, CH3OD, H2O, D2O, 50% D2O-CH3OD were determined at 15.0 and 25.0℃ using conductometric method. Kinetic solvent isotope effects for the solvolyses of para-substituted phenyl chloroformates were 2.39-2.51, 2.21-2.28, and 1.67-1.69 for methanol, 50% aqueous methanol, and water, respectively. The slopes of Hammett plot for solvolysis of para-substituted phenyl chloroformates in methanol, 50% aqueous methanol, and water were 1.49, 1.17 and 0.89, respectively. The Hammett type plot of KSIE, log (KSIE) versus p, can be a useful mechanistic tool for solvolytic reactions. The slopes of such straight lines for para-substituted phenyl chloroformates are almost zero in methanol, 50% aqueous methanol, and water. It was shown that the reaction proceeds via an associative SN2 and/or general base catalysis addition-elimination (SAN) mechanism based on activation parameters, Hammett p values, and slopes of Hammett type plot of KS-IE.

• Bulletin of the Korean Chemical Society
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• 제35권3호
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• pp.753-757
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• 2014

The nucleophilic substitution reactions of Y-aryl N,N-dimethyl phosphoroamidochloridates with substituted anilines and deuterated anilines are kinetically investigated in acetonitrile at $65.0^{\circ}C$. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed based on the positive ${\rho}_{XY}$ value. The deuterium kinetic isotope effects involving deuterated anilines show secondary inverse with all the nucleophiles, rationalized by a dominant backside nucleophilic attack.

• Journal of Applied Biological Chemistry
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• 제44권3호
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• pp.135-139
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• 2001

To observe the changes in isotopic composition (${\delta}^{15}N$) of $NO_3{^-}$ during denitrification, an incubation experiment using soil treated with nitrification inhibitor (2-chloro-6-trichloromethyl-pyridine) under water-saturated condition was conducted for 153 h. The $NO_3-N$ concentration decreased from 73.3 to $20.6mg\;kg^{-1}$ during the incubation period, with denitrification rate constant of $0.00905h^{-1}$, and ${\delta}^{15}N$ values of $NO_3-N$ increased from +0.9 to +25.5‰ with decreasing the $NO_3-N$ concentration. The increase in the ${\delta}^{15}N$ values of $NO_3-N$ is due to kinetic isotope fractionation, which always results in $^{15}N$ enrichment of the substrate. The isotopic fractionation factor calculated in this study was 1.0196, an indication that 1.96% more $^{14}NO_3{^-}$ reacted at a given time interval than a comparable number of $^{15}NO_3{^-}$. The ${\delta}^{15}N$ values measured through the incubation study showed a good agreement with the results calculated from the Fochts isotope fractionation model. Our results suggest that when the ${\delta}^{15}N$ of $NO_3{^-}$ is used for tracing the fate of N, the kinetic isotope fractionation associated with denitrification must be taken into consideration.

• Bulletin of the Korean Chemical Society
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• 제30권12호
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• pp.2909-2912
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• 2009

The amines studied in this study are less reactive toward ethyl propiolate (3) in MeCN than in H$_2$O although they are 7 to 9 pK$_a$ units more basic in the aprotic solvent. The reactivity of morpholine and deuterated morpholine toward 3 is found to be identical, indicating that proton transfer occurs after rate-determining step (RDS). The fact that kinetic isotope effect is absent excludes a stepwise mechanism in which proton transfer occurs in RDS as well as a concerted mechanism in which nucleophilic attack and proton transfer occur concertedly through a 4-membered cyclic transition state (TS). Thus, the reactions have been concluded to proceed through a stepwise mechanism in which proton transfer occurs after RDS. Brønsted-type plots are linear with small ${\beta}_{nuc}$ values, i.e., ${\beta}_{nuc}$ = 0.29 in H$_2$O and ${\beta}_{nuc}$ = 0.51 in MeCN, indicating that bond formation is not advanced significantly in RDS. The small ${\beta}_{nuc}$ value also supports the conclusion drawn from the study of kinetic isotope effect.

• Bulletin of the Korean Chemical Society
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• 제33권10호
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• pp.3274-3278
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• 2012

The kinetic studies on the reactions of phenyl N-phenyl phosphoramidochloridate (8) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) have been carried out in acetonitrile at $60.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are huge secondary inverse ($k_H/k_D$ = 0.52-0.69). A concerted mechanism is proposed with a backside attack transition state (TS) on the basis of the secondary inverse DKIEs and the variation trends of the $k_H/k_D$ values with X. The degree of bond formation in the TS is really extensive taking into account the very small values of the DKIEs. The steric effects of the two ligands on the rates are extensively discussed for the aminolyses of the chlorophosphate-type substrates on the basis of the Taft equation.

• Bulletin of the Korean Chemical Society
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• 제34권10호
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• pp.2989-2994
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• 2013

The solvolysis rate constants of 3,4- (1) and 3,5-dimethoxybenzoyl (2) chlorides were measured in various pure and binary solvents at $25.0^{\circ}C$, and studied by application of the extended Grunwald-Winstein (G-W) equation, kinetic solvent isotope effect in methanolysis and activation parameters. The solvolysis of 1 was interpreted as the unimolecular pathway due to a predominant resonance effect from para-methoxy substituent like 4-methoxybenzoyl chloride (3), while that of 2 was evaluated as the dual mechanism, with unimolecular or bimolecular reaction pathway according to the character of solvent systems (high electrophilic/nucleophilic) chosen, caused by the inductive effect by two meta-methoxy substituents, no resonance one. In the solvolyses of 1 and 2 with two $-OCH_3$ groups, the resonance effect of para-methoxy substituent is more important to decide the mechanism than the inductive effect with other corresponding evidences.

• Bulletin of the Korean Chemical Society
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• 제34권4호
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• pp.1096-1100
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• 2013

The kinetic studies on the reactions of O-methyl (1), O-propyl (3) and O-isopropyl (4) phenyl phosphonochloridothioates with substituted anilines and deuterated anilines have been carried out in acetonitrile at $55.0^{\circ}C$. A concerted $S_N2$ mechanism is proposed for the anilinolyses of 1, 3 and 4. The anilinolysis rates of the phosphonochloridothioates are predominantly dependent upon the steric effects over the inductive effects of the two ligands. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are primary normal with 1 and 3, while secondary inverse with 4. Primary normal and secondary inverse DKIEs are rationalized by frontside and backside nucleophilic attack transition state, respectively. The DKIEs of the phosphonochloridothioates do not have any consistent correlations with the two ligands.

• Bulletin of the Korean Chemical Society
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• 제32권10호
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• pp.3799-3801
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• 2011