• BMB Reports
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• v.39 no.2
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• pp.167-170
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• 2006

Bovine adenosine deaminase undergoes a nondenaturational conformational change at $29^{\circ}C$ upon heating which is characterized by a large increase in heat capacity. We have determined the transition state thermodynamics of the conformational change using a novel application of differential scanning calorimetry (DSC) which employs very slow scan rates. DSC scans at the conventional, and arbitrary, scan rate of $1^{\circ}C/min$ show no evidence of the transition. Scan rates from 0.030 to $0.20^{\circ}C/min$ reveal the transition indicating it is under kinetic control. The transition temperature $T_t$ and the transition temperature interval ${\Delta}T$ increase with scan rate. A first order rate constant $k_1$ is calculated at each $T_t$ from $k_1\;=\;r_{scan}/{\Delta}T$, where $r_{scan}$ is the scan rate, and an Arrhenius plot is constructed. Standard transition state analysis reveals an activation free energy ${\Delta}G^{\neq}$ of 88.1 kJ/mole and suggests that the conformational change has an unfolding quality that appears to be on the direct path to the physiological-temperature conformer.

• Journal of the Korean Magnetic Resonance Society
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• v.23 no.2
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• pp.40-45
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• 2019

The phase transition temperatures and thermodynamic properties of $(NH_4)_2MnCl_4{\cdot}2H_2O$ grown by the slow evaporation method were studied using differential scanning calorimetry and thermogravimetric analysis. A structural phase transition occurred at temperature $T_{C1}$ (=264 K), whereas the changes at $T_{C2}$ (=460 K) and $T_{C3}$ (=475 K) seemed to be chemical changes caused by thermal decomposition. In addition, the chemical shift and the spin-lattice relaxation time $T_{1{\rho}}$ were investigated using $^1H$ magic-angle spinning nuclear magnetic resonance (MAS NMR), in order to understand the role of $NH_4{^+}$ and $H_2O$. The rise in $T_{1{\rho}}$ with temperature was related to variations in the symmetry of the surrounding $H_2O$ and $NH_4{^+}$.

• Bulletin of the Korean Chemical Society
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• v.30 no.12
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• pp.2973-2978
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• 2009

The decomposition reaction mechanism of $CH_3CF_2O$ radical formed from hydroflurocarbon, $CH_3CHF_2$ (HFC-152a) in the atmosphere has been investigated using ab-initio quantum mechanical methods. The geometries of the reactant, products and transition states involved in the decomposition pathways have been optimized and characterized at DFT-B3LYP and MP2 levels of theories using 6-311++G(d,p) basis set. Calculations have been carried out to observe the effect of basis sets on the optimized geometries of species involved. Single point energy calculations have been performed at QCISD(T) and CCSD(T) level of theories. Out of the two prominent decomposition channels considered viz., C-C bond scission and F-elimination, C-C bond scission is found to be the dominant path involving a barrier height of 12.3 kcal/mol whereas the F-elimination path involves that of a 28.0 kcal/mol. Using transition-state theory, rate constant for the most dominant decomposition pathway viz., C-C bond scission is calculated at 298 K and found to be 1.3 ${\times}$ 10$^4s{-1}$. Transition states are searched on the potential energy surfaces involving both decomposition channels and each of the transition states are characterized. The existence of transition states on the corresponding potential energy surface are ascertained by performing Intrinsic Reaction Coordinate (IRC) calculation.

• Electrical & Electronic Materials
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• v.9 no.4
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• pp.404-409
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• 1996

The structural and electric properties of $Y_{1-x}$YbF$_{x}$Ba$_{2}$Cu$_{3}$O$_{7-y}$(x=0.0, 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6) have been investigated by using XRD(X-ray diffraction), TMA(thennomechanical analysis), NMR(nuclear magnetic resonance) analysis and four probe method. $Y_{1-x}$YbF$_{x}$Ba$_{2}$Cu$_{3}$O$_{7-y}$ samples were prepared by conventional solid-state reaction method using $Y_{2}$O$_{3}$, BaCO$_{3}$, CuO and YbF$_{3}$ power. TMA and high temperature XRD results shows that orthorhombic to tetragonal phase transition occurs in the unfluorinated 1-2-3 sample while the phase change is not observed in the fluorinated 1-2-3 samples. Superconducting transition temperature(T$_{c}$) increases with increasing YbF$_{3}$ content ; T$_{c}$, of the sample reaching maximum of 102K for x=0.3, and then decreases with further increasing YbF$_{3}$ content. The structural analysis and T$_{c}$ results shows that the fluorine doping stabilize the orthorhombic phase, together with the increase in T$_{c}$.}$ c/.TEX> c/.

• Bulletin of the Korean Chemical Society
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• v.29 no.6
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• pp.1167-1172
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• 2008

We investigated the glass transition temperatures ($T_g$) of dendrons consisting of conformationally mobile aliphatic polyether dendritic cores plus glassy peripheral polystyrenes (PSs), and linear PSs in the molecular weight range of 1000-8500 g/mol. We compared their $T_g$ behavior depending on their polymeric architecture. The linear PSs show a typical growth of $T_g$ up to 92.5 ${^{\circ}C}$ as the molecular weight increases to 8300 g/mol, while the dendrons display nearly constant $T_g$ values of 58-61 ${^{\circ}C}$, despite the increase of molecular weight with each generation. The striking contrast of Tg behavior would be mainly attributed to the fact that the dendrons keep the ratio of $N_e$/M ($N_e$: number of peripheral chain ends, M: molecular weight) over all the generations. Additionally, for the influence of dendritic spacers on glass transition temperature we prepared dimeric PSs with different linkage groups such as aliphatic ether, ester and amide bonds. We found that the dimer with the ether spacer exhibited the lowest glass transition at 55.4 ${^{\circ}C}$, while the amide linked dimer showed the highest glass transition temperature at 74.2 ${^{\circ}C}$. This indicates that the peripheral PS chains are effectively decoupled by the conformationally flexible ether spacer. The results from this study demonstrated that polymeric architecture and dendritic core structures play a crucial role in the determination of glass transition behavior, providing a strategy for the systematic engineering of polymer chain mobility.

• Food Science and Biotechnology
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• v.14 no.2
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• pp.301-303
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• 2005

State diagram of highly concentrated branched oligosaccharides (HBOS) was constructed to better understand phase behavior of mixtures with different size of oligosaccharides. It showed dramatic plasticizing effect on glass transition, which was successfully described based on Couchman-Karasz equation model. $T_g$' estimated from state diagram corresponded well with previous empirical data measured by maximum ice formation through isothermal holding (annealing) process. Estimated $T_g$' and $C_g$' values were $-36.3^{\circ}C$ and 79.99%, respectively. $T_g$' value of HBOS was approximately $10^{\circ}C$ higher than that of sucrose, while $C_g$' value was similar to those of general carbohydrate materials, which could be useful for applications in frozen system.

• Preventive Nutrition and Food Science
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• v.15 no.4
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• pp.356-359
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• 2010

Glass transition phenomena in nine Korean pure honeys (moisture content 18.3~20.1%) and honey-water mixtures by different water contents (0, 2, 5, and 10% w/w) were investigated with modulated different scanning calorimetry (MDSC). The total, reversing, and non-reversing heat flows were quantified during heating using MDSC. Glass transition was observed from reversing heat flow separated from the total heat flow. The glass transition temperatures ($T_g$) of pure honeys, which are in the range of $-42.7^{\circ}C$ to $-50.0^{\circ}C$, varied a lot with low determination coefficient ($R^2$=0.63), whereas those of honey-water mixtures decreased with a decrease in honey content. The $T_g$ values were also more significantly different among honey-water mixtures when compared to pure honeys, indicating that in the honey-water mixture system the $T_g$ values appear to be greatly dependent on moisture content. The measured heat capacity change (${\Delta}C_p$) was not influenced by moisture content.

• Bulletin of the Korean Chemical Society
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• v.32 no.2
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• pp.451-454
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• 2011

The traditional BCS superconductors $AOs_2O_6$ (A=K, Rb, and Cs) were investigated to find the relationship between their structures and superconducting transition temperatures. The $T_c$ decreases with increasing the unit cell parameter of $AOs_2O_6$. This is in contrast to the case of conventional BCS superconductivity in a single bond model, where $T_c$ may increase with increasing the the unit cell parameter since the DOS at Fermi level increases as the unit cell parameter increases. Instead, the $T_c$ of a $\beta$-pyrochlore oxide is proportional to the lattice softness of the compound.

• Journal of the Korean Society for Heat Treatment
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• v.14 no.6
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• pp.345-349
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• 2001

This study has investigated the effect of thermal stability and mechanical property of $Fe_{80-X}P_{10}C_6B_4M_X$(X=2, 4, 6, M=transition metal) amorphous alloys fabricated by the melt-spun process. The glass transition temperature($T_g$), crystallization temperature($T_x$) and hardness increase with decreasing electron concentration (e/a) from about 7.38 to 7.18. The decrease of e/a implies the increase in the attractive bonding state between the M elements and other constituent element. The decrease in a/e leads to the enhancement of the attractive bonding state among the constituent elements which is favorable for the increase in $T_g$, $T_x$ and hardness.

• Journal of the Korean Magnetic Resonance Society
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• v.21 no.2
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• pp.63-66
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• 2017

The $^{14}N$ NMR spectra for $(NH_4)_2SO_4$ crystals were obtained near the phase transition temperature $T_C=223K$, and were found to precisely reflect the symmetry change in the crystal at this first-order phase transition. Changes in the resonance frequencies near $T_C$ were attributed to the structural phase transition. In the ferroelectric and paraelectric phases, two inequivalent NH4 groups were distinguished in the $^{14}N$ NMR spectra. The two types, $NH_4$(1) and $NH_4$(2), have slightly different local environments. Consequently, we conclude that the phase transition is caused by the change in the environment of the $^{14}N$ nuclei in the $NH_4$ groups, rather than by the $SO_4$ groups.