• The Journal of the Acoustical Society of Korea
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• 제25권1E호
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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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• 제10권3호
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• pp.273-278
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• 1989

The gas-phase reactions of methyl formate with anions, $-NH_2,\;-OH,\;-CH_2CN$, are studied theoretically using the AM1 method. Stationary points are located by the reaction coordinate method, refined by the gradient norm minimization and characterized by the determination of Hessian matrix. Potential energy profiles and the stationary point structures are presented for all conceivable processes. Four reaction paths are found to be possible: formyl proton and methyl proton abstractions, carbonyl addition, and $S_N2$ process. For the most basic anion $-NH_2$ the proton abstraction path is favored, while in other case, $OH\;and\;-CH_2CN$, the carbonyl addition paths are favored. In all cases the $S_N2$ process is the most exothermic, but due to the relatively high activation barrier the process can be ruled out.

• Bulletin of the Korean Chemical Society
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• 제30권12호
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• pp.3133-3136
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• 2009

• Bulletin of the Korean Chemical Society
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• 제27권11호
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• pp.1903-1906
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• 2006

• Bulletin of the Korean Chemical Society
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• 제34권7호
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• pp.1961-1966
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• 2013

Theoretical investigations have been performed for the ground state ($S_0$) and the first excited state ($S_1$) of the hydrogen bonded green fluorescent protein (GFP) model. The potential energy surface (PESs) of $S_0$ was obtained by B3LYP method and that of $S_1$ was obtained by CIS method. Based on the relative stabilities of species and the energy barriers for the proton transfer, it was found that proton transfer could take place both under the ground state and the first excited state. As determined by the proton motions along the reaction coordinate, both the ground state proton transfer (GSPT) and the excited state proton transfer (ESPT) are considered as a concerted and asynchronous process.

• Bulletin of the Korean Chemical Society
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• 제28권12호
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• pp.2343-2353
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• 2007

We report the application of time-dependent density functional theory (TDDFT) to the calculation of potential energy profile relevant to the excited state intramolecular proton transfer (ESIPT) processes in title molecules. The TDDFT single point energy calculations along the reaction path have been performed using the CIS optimized structure in the excited state. In addition to the Stokes shifts, the transition energies including absorption, fluorescence, and 0-0 transition are estimated from the TDDFT potential energy profiles along the proton transfer coordinate. The excited state TDDFT potential energy profile of SA and 3ASA resulted in very flat function of the OH distance in the range ROH = 1.0-1.6 A, in contrast to the relatively deep single minimum function in the ground state. Furthermore, we obtained very shallow double minima in the excited state potential energy profile of SA and 3ASA in contrast to the single minimum observed in the previous work. The change of potential energy profile along the reaction path induced by the substitution of electron donating groups (-NH2 and -OCH3) at different sites has been investigated. Substitution at para position with respect to the phenolic OH group showed strong suppression of excited state proton dislocation compared with unsubstitued SA, while substitution at ortho position hardly affected the shape of the ESIPT curve. The TDDFT results are discussed in comparison with those of CASPT2 method.

• 한국세라믹학회지
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• 제37권3호
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• pp.271-279
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• 2000

5 m/o Yb-doped SrCeO3 proton conductor was prepared by a solid state reaction method and its total electriccal conductivity measured as a function of both oxygen partial pressure and water vapor partial pressure in the temperature range of 500~100$0^{\circ}C$. From the total conductivity have been deconvoluted the partial conductivities of oxide ions, protons, and holes, respectively, on the basis of the defect model proposed. The equilibrium constant of hydrogen-dissolution reaction, proton concentration, and mobilities of oxygen vacancies and protons have subsequently been evaluated. It is verified that SrCe1-xYbxO3 is a mixed conductor of holes, protons and oxide ions and the proton conduction prevails as temperature decreases and water vapor pressure increases. The heat of water dissolution takes a representative value of $\Delta$HoH=-(140$\pm$20) kJ/mol-H2O, but tends to be less negative with increasing temperature. Migration enthalpies of proton and oxygen vacancy are extracted as 0.83$\pm$0.10 eV and 0.81$\pm$0.01 eV, respectively.

• Bulletin of the Korean Chemical Society
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• 제24권11호
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• pp.1675-1679
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• 2003

The photodynamics of excited-state intramolecular proton transfer reaction of 1-hydroxyanthraquinone (1-HAQ) and 1-deuterioanthraquinone was investigated in toluene with time-resolved emission and femtosecond transient transmittance techniques at room temperature. The temporal profiles of transient transmittance of 1-HAQ could be well described with multi-decaying time constants. The ultrafast time constant within ca. 260 fs reflects the dynamics of proton transfer. The decay component of 2 ps is assigned to an additional proton translocation process induced by the intramolecular vibrational relaxation, whereas the decay component of 18 ps is assigned to the vibrational cooling process, while the long component (200 ps) can be explained in terms of the relaxation from excited-state keto-tautomer to its ground state. Time-resolved anisotropy decay dynamics and isotope effects on the photodynamics reveals that the ESIPT from enol-tautomer to keto-one of 1-HAQ is barrierless reaction and coupled to a vibrational relaxation process.

• Nuclear Engineering and Technology
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• 제54권8호
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• pp.3006-3016
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• 2022

In this study, the images of specific prompt gamma (PG)-rays of 719 keV emitted from proton-boron reactions were analyzed using single-photon emission computed tomography (SPECT). Quantitative evaluation of the images verified the detection of anatomical changes in tumors, one of the important factors in daily adaptive proton therapy (DAPT) and verified the possibility of application of the PG-ray images to DAPT. Six scenarios were considered based on various sizes and locations compared to the reference virtual tumor to observe the anatomical alterations in the virtual tumor. Subsequently, PG-rays SPECT images were acquired using the modified ordered subset expectation-maximization algorithm, and these were evaluated using quantitative analysis methods. The results confirmed that the pixel range and location of the highest value of the normalized pixel in the PG-rays SPECT image profile changed according to the size and location of the virtual tumor. Moreover, the alterations in the virtual tumor size and location in the PG-rays SPECT images were similar to the true size and location alterations set in the phantom. Based on the above results, the tumor anatomical alterations in DAPT could be adequately detected and verified through SPECT imaging using the 719 keV PG-rays acquired during treatment.

• Bulletin of the Korean Chemical Society
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• 제31권2호
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• pp.365-371
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• 2010

The multiconfiguration molecular mechanics (MCMM) algorithm was used to generate potential and vibrationally adiabatic energy surfaces for excited-state tautomerization in the 1:1 7-azaindole:$H_2O$ complex. Electronic structures and energies for reactant, product, transition state were computed at the CIS/6-31G(d,p) level of theory. The potential and vibrationally adiabatic energies along the reaction coordinate were generated step by step by using 16 high-level Shepard points, which were computed at the CIS/6-31G(d,p) level. This study shows that the MCMM method was applied successfully to make quite reasonable potential and adiabatic energy curves for the excited-state double proton transfer reaction. No stable intermediates are present in the potential energy curve along the reaction coordinate of the excited-state double proton transfer in the 1:1 7-azaindole:$H_2O$ complex, indicating that these two protons are transferred concertedly. The change in the bond distances along the reaction coordinate shows that two protons move very asynchronously to make an $H_3O^+$-like moiety at the transition state.