• 대한한의학회지
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• 제29권1호
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• pp.117-133
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• 2008

Objectives : Since ancient times, Koreans have applied medicinal spabaths for treatment of various diseases. The objective of this study was to investigate the effect of strontium, one of the common ingredients of such baths, experimentally on acute skin barrier damage. Materials and Methods : Male hairless mice, average weight 20g, were divided into six groups. Each group consisted of five mice. The first was the normal, non-treated group. The second was the control group with acute skin barrier damage intentionally induced by TS. The third was the Ba-Sr1 group bathed in 1mg/L strontium chloride before and after inducing acute skin barrier damage by TS. The fourth was the Ba-Sr7 group bathed in 7mg/L strontium chloride before and after inducing acute skin barrier damage by TS. The fifth was the Sr1 group bathed in 1mg/L of strontium chloride only after intentionally inducing acute skin barrier damage by TS. The sixth was the Sr7 group bathed in 7mg/L of strontium chloride only after intentionally inducing acute skin barrier damage by TS. External changes of skin, skin erythema level, transepidermal water loss level, and GOT and GPT level of each group were checked immediately before and after TS, 3 hrs, 5 hrs and 24 hrs after inducing acute skin barrier damage. Then, tissue samples were made and examined for damage to epithelial cells, stratum corneum, change of mucous polysaccharide in dermis and amount of mast cells. Statistical analysis was performed by one way-ANOVA, Scheffe and Duncan for a post hoc test and pairwise comparison for comparing for difference between each time. Statistical significance was achieved if the probability was less than 5% (p<0.05) Results : 1. From skin erythema and TEWL level indicating the function of the skin barrier, we can know that it is helpful to the skin barrier to bathe in a water solution including a low concentration of strontium. 2. In the control group with acute skin barrier damage induced by TS, skin barrier damage persisted until 3-5 hrs and recovered after 5-24 hrs. Differently from the control group, in the case of taking a bath in a water solution including strontium, skin barrier damage recovered after only 3-5 hrs. Therefore, the bath with a water solution including strontium can promote recovery of the skin barrier. 3. Bathing in water solution including a higher concentration of strontium was more beneficial to recovery of skin barrier damage. 4. There was no influence on serum GOT and GPT from bathing in a water solution including strontium. Conclusions : The strontium was effective for recovery and mitigation of acute skin barrier damage induced by tape stripping. I suggest that strontium (Sr) can be used as an external treatment medicine, addedinto bath water to treat acute skin barrier damage.

• Bulletin of the Korean Chemical Society
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• 제17권9호
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• pp.849-853
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• 1996

Hetero Dieis-Alder reactions containing phosphorus atom at various positions of diene and dienophile as well as standard Dieis-Alder reaction between ethylene and cis-l,3-butadiene have been studied using ab initio method. Activation energy showed a good linear relationship with the FMO energy gap between diene and dienophile, which can be normally used to explain Dieis-Alder reactivity. Since π-bond cleavage and σ-bonds formation occur concertedly at the TS, geometrical distortion of diene and dienophile from the reactant to the transition state is the source of barrier. Based on the linear correlations between activation barrier and deformation energy, and between deformation energy and π-bond order change, it was concluded that the activation barrier arises mainly from the breakage of π-bonds in diene and dienophile. Stabilization due to favorable orbital interaction is relatively small. The geometrical distortions raise MO levels of the TS, which is the origin of the activation energy. The lower barrier for the reactions of phosphorus containing dienophile (reactions C, D, and E) can be explained by the electronegativity effect of the phosphorus atom.

• Bulletin of the Korean Chemical Society
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• 제35권2호
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• pp.546-550
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• 2014

Relative reactivity of various carbonyl and acid derivatives in MPV-type (Meerwein-Ponndorf-Verley) reduction with an DIBAL(F) model has been studied via DFT and MP2 methods. Free energies of initial adduct formation (-Gadd) of DIBAL(F) model and carbonyls are in the order of amide < ester < aldehyde < ketone < acid chloride; in the alan-amide adduct, the developed positive charge at carbonyl carbon is expected to be stabilized by amide resonance, but in the acid chloride adduct it is destabilized by inductive effect of chloride. However the TS barrier energies (${\Delta}G_{TS}$) for the MPV-type hydride reduction of the carbonyl adducts are in the order of aldehyde < ketone < acid chloride << ester < amide; presumably decreasing order of electrophilicity of carbonyl carbon at adducts, which is well correlated with experimental data. It is noted that the relative reactivity of carbonyl derivatives in MPV-type reduction with DIBAL(X) is not governed by the alan-adduct formation energies, but follows the order of electrophilicity of carbonyl carbon of transition states.

• 한국재료학회지
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• 제25권10호
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• pp.571-576
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• 2015

The effects of coating thickness on the delamination and fracture behavior of thermal barrier coating (TBC) systems were investigated with cyclic flame thermal fatigue (FTF) and thermal shock (TS) tests. The top and bond coats of the TBCs were prepared by electron beam-physical vapor deposition and low pressure plasma spray methods, respectively, with a thickness ratio of 2:1 in the top and bond coats. The thicknesses of the top coat were 200 and $500{\mu}m$, and those of the bond coat were 100 and $250{\mu}m$. FTF tests were performed until 1140 cycles at a surface temperature of $1100^{\circ}C$ for a dwell time of 5 min. TS tests were also done until more than 50 % delamination or 1140 cycles with a dwell time of 60 min. After the FTF for 1140 cycles, the interface microstructures of each TBC exhibited a sound condition without cracking or delamination. In the TS, the TBCs of 200 and $500{\mu}m$ were fully delaminated (> 50 %) within 171 and 440 cycles, respectively. These results enabled us to control the thickness of TBC systems and to propose an efficient coating in protecting the substrate in cyclic thermal exposure environments.

• Food Science and Biotechnology
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• 제18권5호
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• pp.1155-1160
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• 2009

Poly(lactide) (PLA)-coated paperboards were prepared by solution coating and thermo-compression coating methods and their effect of coating on the packaging properties such as tensile, water resistance, water vapor barrier, and heat sealing properties was tested. Compared with uncoated control paperboard, tensile strength (TS) of PLA-coated paperboard increased profoundly (2.2-2.6 folds) with slight increase in elongation at break (E). Water absorptiveness (WA) of the paperboard decreased 74-170 folds and water vapor permeability (WVP) decreased 6.3-22.1 folds by coating with PLA, which indicates an increase in the hydrophobicity of the surface of paperboard. Compared with polyethylene (PE)-coated paperboard, both PLA-coated paperboard exhibited 2.3 time higher heat sealing strength. In addition, the PLA-coated paperboards showed equal or higher wet TS than PE-coated paperboard. All the test results showed that the paperboard coated by the thermo-compression coating method was similar to or better than those of coated by the solution coating method.

• Bulletin of the Korean Chemical Society
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• 제7권5호
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• pp.391-395
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• 1986

MNDO calculations were carried out to determine reactant complexes and transition states of the $S_N2$ reactions of $CH_3X\;+\;Y^-\;{\to}\;CH_3Y\;+\;X^-$ where X = F, Cl, CN and Y = CN, OH, F, Cl. The leaving group ability was found to vary inversely with the activation barrier, which in turn was mainly ascribable to the deformation energies accompanied with bond stretching of C-X bond and inversion of $CH_3$ group. The nucleophilicity was shown to be in the order $Cl^->F^->OH^->CN^-$ but the effect on the activation barrier was relatively small compared with that of the leaving group. The bond breaking and bond formation indices and energy decomposition analysis showed that the TS for the reaction of $CH_3$Cl occurs in the early stage of the reaction coordinate relative to that of $CH_3$F. It has been shown that the potential energy surface (PES) diagrams approach can only accommodate thermodynamic effects but fails to correlate intrinsic kinetic effects on the TS structure.

• Bulletin of the Korean Chemical Society
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• 제16권12호
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• pp.1203-1208
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• 1995

Theoretical studies of the effect of the nonleaving group (RY) on the breakdown mechanism of the tetrahedral anionic intermediate, T-, formed by the addition of a less basic phenoxide nucleophile (X) to phenyl benzoates with a more basic phenoxide leaving group (Z) have been carried out using the PM3 MO method. The identity acyl transfer reactions (X=Z) are facilitated by an electron-withdrawing RY whereas they are inhibited by an electron-donating RY group. The results of non-identity acyl transfer reactions indicate that a more electron-donating RY group leads to a greater lowering of the higher barrier, TS2, with a greater degree of bond cleavage, and a greater negative charge development on the phenoxide oxygen atom, whereas the opposite is true for a more electron-withdrawing RY group, i.e., leads to a greater lowering of the lower barrier, TS1. The results provide theoretical basis for the signs of ρXY(>0) and ρYZ(<0) observations.

• Bulletin of the Korean Chemical Society
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• 제6권6호
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• pp.362-366
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• 1985

The hydrogen atom transfer reaction between substituted methane, $CH_3X,$ and its radical, $CH_2X(X=H,F,CH_3,CN,OH\;and\;NH_2$ was studied by MINDO/3 method. The transition state(TS) structure and energy barriers were determined and variation of the transition state and of the reactivity due to the change of X were analyzed based on the potential energy surface characteristics. It was found that the greater the radical stabilization energy. the looser the TS becomes; the TS occurs at about 15% stretch of the C-H bond, which becomes longer as the radical stabilization energy of $CH_2X$ increasers. The intrinsic barrier, ${\Delta}E*_{x.x},$ of the reaction with X was found to increase in the order $H The degree of bond stretch of the C-H bond stretch of the C-H bond at the TS also had the same order indicating that the homolytic bond cleavage of the C-H bond is rate-determining. Orbital interactions at the TS between LUMO of the fragment $C{\ldots}H{\ldots}C$ and the symmetry adapted pair of nonbonding, $n{\pm}(=n_1{\pm}n_2),$ or pi orbitals of the two X atoms were shown to be the dominant contribution in determining tightness or looseness of the TS. The Marcus equation was shown to apply to the MINDO/3 barriers and energy changes of the reaction.

• Bulletin of the Korean Chemical Society
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• 제22권7호
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• pp.732-738
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• 2001

The cross second-derivative of the activation energy,${\theta}$G${\neq}$ , with respect to the two component thermodynamic barriers, ${\theta}$G˚X and ${\theta}$G$^{\circ}C$Y, can be given in terms of a cross-interaction constant (CIC), $\betaXY(\rhoXY)$, and also in terms of the intrinsic barrier,${\theta}$G${\neq}$ , with a simple relationship between the two: $\betaXY$ = $-1}(6${\theta}$G${\neq}$).$ This equation shows that the distance between the two reactants in the adduct (TS, intermediate, or product) is inversely related to the intrinsic barrier. An important corollary is that the Ritchie N+ equation holds (for which $\betaXY$ = 0) for the reactions with high intrinsic barrier. Various experimental and theoretical examples are presented to show the validity of the relationship, and the mechanistic implications are discussed.

• 대한화학회지
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• 제34권3호
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• pp.239-247
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• 1990

기체상 $S_N2$ 반응의 형태는 중성 2분자반응, 용매화반응, 이온반응 등으로 나눌 수 있으며, 메카니즘적으로 중성 2분자 반응은 retention 생성물을 만들며 이온반응은 inversion 생성물을 만든다. 한편 용매인 물 한 분자에 의하여 6- 중심 건이상태를 거치는 용매화반응의 경우는 친핵체(또는 이탈기)및 치환기에 의한 전자효과와 입체효과에 따라 두 생성물이 경쟁적으로 만들어진다. 여기에서 얻어진 결과를 이용하여 이온반응의 경우, 중앙 methly group을 매우 bulky 하게 하고 이탈기 능력을 크게 해줌과 동시에 음이온인 친핵체의 하전을 분산시켰을 때 inversion과 retention TS 사이의 에너지 차이가 아주 작게 나타났다. $S_N2$ 반응의 반응중심을 보다 더 큰 2주기 원소로 바꾸었을 때, 5가의 전이상태에 미치는 입체장애가 작아지므로 활성화에너지 장벽이 낮아진다. 반면, 같은 주기에서 원자의 크기가 작아지면 에너지 장벽은 올라간다. B원자의 경우 에너지 장벽이 가장 낮은데, 그것은 C와 N 원자보다도 더 크며 또한 4가의 전이상태를 이루므로 입체장애가 거의 무시되기 때문이다.