• Mass Spectrometry Letters
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• v.2 no.3
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• pp.73-75
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• 2011

In the collisionally-activated dissociation of the proton-bound cluster ions of DNA base guanine (G) and cytosine (C), $G{\bullet}{\bullet}H^+{\bullet}{\bullet}C$, the abundance of [$CH^+$] ions was found to be higher than that of [$GH^+$] despite the fact that G has a higher proton affinity than C. This unexpected observation seems to demonstrate another example that the simple kinetic method scheme does not work. We suggest that a kinetic factor or detailed dynamics governing the proton transfer and dissociation should be carefully considered in the applications of the kinetic method to the proton affinity measurements.

• The Journal of the Acoustical Society of Korea
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• v.16 no.1E
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• pp.24-28
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• 1997

Ultrasonic relaxation measurements for imidazole and its derivative in phosphate buffer exhibit a high peak of absorption at neutral pH. Near neutral pH, protolysis and hydrosis may be neglected and the essential reaction only consists of a direct proton-exchange. The kinetics constants and the volume changes for the proton transfer reaction with the protonated imidazole and 2-methylimidazole have been determined at 25℃. The kinetics constants are 7.2×108s-1M-1for imidazole and 1.7×108s-1M-1 for 2-methylimidazole. The kinetics constants are used to estimate the spectrum of relaxation times and acoustic relaxation amplitude associated with intermolecular and intramolecular proton-exchange reactions in bilogical media. It is concluded that the magnitude of the acoustic absorption reasonalbly attributable to the perturbation of proton-transfer equilibria between imidazole and inorganic phosphate is comparable in magnitude with the acoustic absorption observed in some intact tissues.

• Journal of Electrochemical Science and Technology
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• v.1 no.2
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• pp.121-126
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• 2010

An amperometric ascorbic acid selective sensor utilizing the transfer reaction of proton liberated from the dissociation of ascorbic acid in aqueous solution across an elliptic micro-hole water/organic gel interface is demonstrated. This redox inactive sensing platform offers an alternative way for the detection of ascorbic acid to avoid a fouling effect which is one of the major concerns in redox based sensing systems. The detection principle is simply measuring the current change with respect to the assisted transfer of protons by a proton selective ionophore (e.g., ETH 1778) across the micro-hole interface between the water and the polyvinylchloride-2-nitrophenyloctylether gel phase. The assisted transfer reaction of protons generated from ascorbic acid across the polarized micro-hole interface was first characterized using cyclic voltammetry. An improved sensitivity for the quantitative analysis of ascorbic acid was achieved using differential pulse stripping voltammetry with a linear response ranging from 1 to $100\;{\mu}M$ concentrations of ascorbic acid. As a demonstration, the developed sensor was applied for analyzing the content of vitamin-C in different types of commercial pharmaceutical tablets and syrups, and a satisfactory recovery from these samples were also obtained.

• Bulletin of the Korean Chemical Society
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• v.30 no.12
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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.

• Journal of the Korean Ceramic Society
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• v.46 no.6
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• pp.695-699
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• 2009

We studied the transfer of oxygen vacancy and proton in Y-doped BaZr$O_3$ (BYZ) using density functional theory (DFT). An oxygen vacancy was generated in the $2{\times}2{\times}2$ BYZ superstructure by replacing two Zr atoms with two Y atoms to satisfy the charge neutrality condition. The O vacancy transfer between the first and second nearest O atom sites from a Y atom showed the lowest activation energy barrier of 0.42 eV, compared to the other transfers between first and first, and second and second in the superstructure. Two protons were inserted in the structure by adding a proton and hydroxyl that were supplied by the dissociation of a water molecule. The two protons bonded to the first and second nearest O atoms were energetically the most favorable. The activation energy barrier for a proton transfer in the structure was 0.51 eV, when either proton transferred to its neighbor O atom. This value was well matched with the experimentally determined one.

• Journal of the Korean Ceramic Society
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• v.47 no.5
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• pp.474-478
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• 2010

We studied the energy barrier for proton conduction with volume variation in $BaZrO_3$ using a first principles study to investigate an optimum volume for the proton conduction. The volume increase of $BaZrO_3$ was expected to decrease the energy barrier for proton rotation and to increase that for proton transfer, and these trends could be extrapolated when the volume was decreased. However, the energy barriers for the proton transfer with the volume decrease were increased, while all the other energy barriers varied as expected. We could explain this unexpected behavior by the bent Zr-O-Zr structure, when the volume was decreased.

• Bulletin of the Korean Chemical Society
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• v.26 no.11
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• pp.1706-1710
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• 2005

The excited-state intramolecular proton transfer (ESIPT) fluorescence in the 2-(2'-hydroxyphenyl)benzoxazole (HBO) derivatives with different electron donor and acceptor substituents was studied by spectroscopic and theoretical methods. Changes in the electronic transition, energy levels, and orbital diagrams of HBO analogues were investigated by the semi-empirical molecular orbital calculation and were correlated with the experimental spectral position of ESIPT keto emission. It was found that the presence of substituents, regardless of their nature, resulted in the red-shifted absorption relative to HBO. However, the spectral change of the ESIPT fluorescence was differently affected by the nature of substituent: hypsochromic shift with electron donor and bathochromic shift with electron acceptor.

• Journal of Photoscience
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• v.1 no.1
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• pp.15-23
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• 1994

The absorption and fluorescence spectral properties of piroxicam (PRX) in the hydrogenbonding solvents show the most sensitive dependence on the concentration ranging from 8 x 10$^{_5}$ to 2 x10$^{_5}$ M. These are attributed to both the solvent-mediated ground-state intermolecular proton transfer (GSIerPT) leading to formation of the ground state anion and the excited-state intmmolecular proton transfer (ESIraPT). The concentration dependences of the time-resolved emission kinetics at both room temperature and 77 K have also been investigated. It is shown that in the excited state, the ESIraPT of PRX is the dominant process to form a keto tautomer at the high concentration, whereas at the low concentration the excited-state conformational change of the anion is an additional process leading to formation of a zwitterion. The ESI~PT of PRX in the hydrogenbonding solvent is coupled with the ultrafast excited-state solvent reorganization.

• The Journal of the Acoustical Society of Korea
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• v.25 no.1E
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• pp.14-19
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• 2006

Ultrasonic absorption and velocity spectra in bovine serum albumin (BSA) aqueous solutions have been measured at $20^{\circ}C$ over the frequency range 0.2-3 MHz in the pH range 1.5-13.2. The high-Q ultrasonic resonator and pulse-echo overlap methods were used. At acid pH's, excess absorption over that of pH 7 was explained by double relaxation. The pH dependences of the relaxation frequency and maximum absorption per wavelength, showed that the relaxation at about 200 kHz was related to the expansion of molecules and that about 3 MHz resulted from the proton transfer reaction of carboxyl group. At alkaline pH's, the excess absorption was explained by double relaxation. The relaxation at about 300 kHz was associated with a helix-coil transition, and that about 3 MHz was attributed to the proton transfer reaction of phenolic group. The rate constants and volume changes associated with these processes were estimated.

• Bulletin of the Korean Chemical Society
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• v.35 no.3
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• pp.881-885
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• 2014

Photophysics of 10-hydroxybenzo[h]quinoline (HBQ) has been in controversy, in particular, on the nature of the electronic states before and after the excited state intramolecular proton transfer (ESIPT), even though the dynamics and mechanism of the ESIPT have been well established. We report highly time resolved fluorescence spectra over the full emission frequency regions of the enol and keto isomers and the anisotropy in time domain to determine the accurate rates of the population decay, spectral relaxation and anisotropy decay of the keto isomer. We have shown that the ~300 fs component observed frequently in ESIPT dynamics arises from the $S_2{\rightarrow}S_1$ internal conversion in the reaction product keto isomer and that the ESIPT occurs from the enol isomer in $S_1$ state to the keto isomer in $S_2$ state.