• Bulletin of the Korean Chemical Society
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• 제28권10호
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• pp.1643-1644
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• 2007

• Bulletin of the Korean Chemical Society
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• 제6권5호
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• pp.270-272
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• 1985

The rate constants of the hydrogen-deuterium exchange of 8-CH groups in 5'-rAMP and 5'-GMP were measured by laser Raman spectroscopy. The Arrhenius activation energies calculated from the rate constants measured as a function of temperature were similar for both compounds. However, the effects of pD on exchange rate constants were different for the two compounds. Our kinetic data support the exchange reaction mechanism involving an ylide type intermediate.

• Bulletin of the Korean Chemical Society
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• 제34권5호
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• pp.1401-1406
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• 2013

This study tested the feasibility of observing H/D exchange of intact protein by top-down electron capture dissociation (ECD) mass spectrometry for the investigation of protein structure. Ubiquitin is selected as a model system. Local structural information was obtained from the deuteration levels of c and $z^{\cdot}$ ions generated from ECD. Our results showed that ${\alpha}$-helix region has the lowest deuteration level and the C-terminal fraction containing a highly mobile tail has the highest deuteration level, which correlates well with previous X-Ray and HDX/NMR analyses. We studied site-specific H/D exchange kinetics by monitoring H/D exchange rate of several structural motives of ubiquitin. Two hydrogen bonded ${\beta}$-strands showed similar HDX rates. However, the outer ${\beta}$-strand always has higher deuteration level than the inner ${\beta}$-strand. The HDX rate of the turn structure (residues 8-11) is lower than that of ${\beta}$-strands (residues 1-7 and residues 12-17) it connects. Although isotopic distribution gets broader after H/D exchange which results in a limited number of backbone cleavage sites detected, our results demonstrate that this method can provide valuable detailed structural information of proteins. This approach should also be suitable for the structural investigation of other unknown proteins, protein conformational changes, as well as protein-protein interactions and dynamics.

• Journal of Photoscience
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• 제9권2호
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• pp.299-301
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• 2002

Recent denaturation experiments of bacteriorhodopsin (bR) in the dark and under illumination at high temperatures revealed that irreversible thermal bleaching occurs above ~ 70°C and the preceding reversible structural changes in the dark above 60°C are closely related to irreversible photobleaching observed in the same temperature range (Yokoyama et al. (2002). J Biochem. 131,785). In this study, structural properties of bacteriorhodopsin (bR) at high temperatures were extensively probed by hydroxylamine reactivity with the Schiff base in the dark and hydrogen-deuterium (H-D) exchange in the peptide groups. In the Arrhenius plot from kinetics measurements of the hydroxylamine reaction, a good linear relationship between the reaction time constant and the inverse of the absolute temperature was observed below 60°C, while significant increase started above 60°C, suggesting that remarkable increase in water accessibility of the Schiff base in the temperature region. FT-IR spectroscopic studies on the H-D exchange suggested increase in the deuterium exchanges rate of the peptide hydrogen in the same temperature region.

• Ocean and Polar Research
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• 제37권4호
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• pp.327-332
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• 2015

Isotopic compositions of ice and meltwater play a very crucial role in paleoclimate studies based on ice cores and water resources research conducted in alpine hydrogeology. Better understanding of variations in the stable isotopic compositions of water is required since changes from ice to liquid water are gaining more attention due to recent climate change. In this work, a melting experiment was designed and conducted to investigate how the isotopic compositions of ice vary with time by heat sources, such as solar radiation. We conducted the melting experiment for 22 hours. The discharge rate rose to a maximum value after 258 minutes and gradually declined because we fixed the heat source. The isotopic compositions of meltwater increased linearly or to a second degree polynomial. The linear relationship between oxygen and hydrogen has a slope of 6.8, which is less than that of the Global Meteoric Water Line (8) and higher than a theoretical value (6.3). The deuterium excess decreased when ${\delta}D$ or ${\delta}^{18}O$ increases or vise versa since the slope of the relationship for ice-liquid exchange is less than 8. These findings and the apparatus of the melting experiments will make a helpful contribution to the studies of stable isotopes and the melting process in temperate and polar regions.