• Bulletin of the Korean Chemical Society
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• 제32권12호
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• pp.4347-4351
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• 2011

The nucleophilic substitution reactions of ethylene phosphorochloridate (2) with X-pyridines are investigated kinetically in acetonitrile at $-20.0^{\circ}C$. The free energy correlations for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Ph. Unusual positive ${\rho}_X$ (= +2.49) and negative ${\beta}_X$ (= -0.41) values are obtained with the weakly basic pyridines, and rationalized by the isokinetic relationship with isokinetic temperature at $t_{ISOKINETIC}=6.6^{\circ}C$. The pyridinolysis rate of 2 with a cyclic five-membered ring is forty thousand times faster than its acyclic counterpart (3: diethyl chlorophosphate) because of great positive value of the entropy of activation of 2 (${\Delta}S^{\neq}$ = +49.2 eu) compared to negative value of 3 (${\Delta}S^{\neq}$ = -44.1 eu) over considerably unfavorable enthalpy of activation of 2 (${\Delta}H^{\neq}=28.4\;kcal\;mol^{-1}$) compared to 3 (${\Delta}H^{\neq}=6.3\;kcal\;mol^{-1}$). Great enthalpy and positive entropy of activation are ascribed to sterically congested transition state (TS) and solvent structure breaking in the TS. A concerted mechanism involving a change of nucleophilic attacking direction from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines is proposed.

• 한국표면공학회:학술대회논문집
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• 한국표면공학회 2012년도 춘계학술발표회 논문집
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• pp.333-333
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• 2012

In this study, we investigated morphology of nanotube and micropore on the Ti-25Nb-xHf alloys with Hf contents after anodization. Ti-25Nb-xHf ternary alloys contained from (0~15) wt.% Hf contents were manufactured by vacuum arc-melting furnace. The obtained ingots were homogenized in an argon atmosphere at $1000^{\circ}C$ for 12h and then water quenching. The specimens were cut from ingots to 3mm thickness and first ground and polished using SiC paper (grades from 100 to 2000). 2steps anodization treatments on Ti-25Nb-xHf alloys were carried out at room temperature for experiments. Micro-pore formation was performed in Ca+P mixed solution at 265V for 3min. After that, nanotube formation was in 1M $H_3PO_4$ electrolytes containing 0.8wt.% NaF solutionat 10V for 120min. Morphologies of micropore and nanotube depended on the Hf content in Ti-25Nb-xZr ternary system.

• Bulletin of the Korean Chemical Society
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• 제33권3호
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• pp.1037-1041
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• 2012

The nucleophilic substitution reactions of (2R,4R,5S)-(+)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $5.0^{\circ}C$. The anilinolysis rate of 3 involving a cyclic five-membered ring is considerably fast because of small negative value of the entropy of activation (${\Delta}S^\neq=-2cal\;mol^{-1}\;K^{-1}$) over considerably unfavorable enthalpy of activation (${\Delta}H^\neq=18.0\;kcal\;mol^{-1}$). Great enthalpy and small negative entropy of activation are ascribed to sterically congested transition state (TS) and bulk solvent structure breaking in the TS. A concerted $S_N2$ mechanism with a backside nucleophilic attack is proposed on the basis of the secondary inverse deuterium kinetic isotope effects, $k_H/k_D$ < 1.

• The Korean Journal of Physiology and Pharmacology
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• 제8권4호
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• pp.187-194
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• 2004

Middle cerebral artery occlusion (MCAO) results in cell death by activation of complex signal pathways for cell death and survival. Hypothermia is a robust neuroprotectant, and its effect has often been attributed to various mechanisms, but it is not yet clear. Upstream from the cell death promoters and executioners are several enzymes that may activate several transcription factors involved in cell death and survival. In this study, we immunohistochemically examined the phosphorylation of mitogen-activated protein kinase, extracellular signal-regulated kinase (ERK), c-Jun N-terminal kinase (JNK) and p38 kinase during early period of the ischemic injury, following 2 hours (h) of transient MCAO. Increased phosphorylation of ERK and p38 was observed in the vessels at 3 h, neuron-like cells at 6 and 12 h and glia-like cells at 12 h. Activation of JNK was not remarkable, and a few cells showed active JNK following ischemia. Phosphorylation of Elk-1, a transcription factor, was reduced by ischemic insult. Hypothermia attenuated the activation of ERK, p38 and JNK, and inhibited reduction of Elk-1. These data suggest that signals via different MAPK family members converge on the cell damage process and hypothermia protects the brain by interfering with these pathways.

• 한국재료학회지
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• 제3권4호
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• pp.319-326
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• 1993

Hydroxide법으로 ${\alpha}$-주산산(stannic acid)을 만든후, 하고온도를 $500^{\circ}C$~$1100^{\circ}C$로 조정하여 일차입자(Crystallite)크기가 8-54nm인 $SnO_2$ 분말을 제작하였다. 분말의 입자(drystalite)클기에 따른 분말특성와 $H_2$, CO가스(0.5v/o)에 대한 감응성 미치공기중에서의 저상변화특성에 미치는 영향을 조사하였다. 입자크기가 감소함에 따라, 분말의 FTIR 흡습특성은 증가하였으나, 격자상수는 일정하였다. 후막소자에서, $H_2$가스에 대해 최대감도를 나타내는 온도와 공기중에서 최소저항을 나타내는 온도는 입자크기가 미세해짐에 따라 점차 낮아졌다. 최소저항점과 최대감도점의 온도저하를 산소흡착종의 활성화에너지의 감소라고 유추하였고, 이러한 에너지의 감소가 미세입자에 의한 감도향상요인 중의 한가지라고 제의하였다.

• 한국세라믹학회지
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• 제24권5호
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• pp.417-422
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• 1987

Kinetic studies were made on the thermal decomposition of hydrated magnesium aluminum double sulfate by a nonisothermal TG method. Thermal analyses of the dehydration of tricosahydrate showed that the reaction proceeded via decahydrate to the anhydrous MgAl2(SO4)4 in the range 50$^{\circ}$to 400$^{\circ}C$. Decomposition of MgAl2(SO4)4 occurred as the two-step between 650$^{\circ}$ and 970$^{\circ}C$. Dehydration of MgAl2(SO4)4$.$23H2O and a 2D diffusion controlled with an activation energy of 16.6kcal/mole, respectively. MgAl2(SO4)4 fitted the contracting volume model with an activation energy of 10.5kcal/mole, and MgSO4 fitted a contracting area model with an activation of 4.5kcal/mole.

• Biomolecules & Therapeutics
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• 제16권1호
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• pp.1-8
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• 2008

Mitochondria are important sensor of apoptosis. $H_2O_2-induced$ cell death rate was enhanced by serum deprivation. In this study, we investigated whether serum deprivation using 0.5 or 3 % FBS induces apoptotic cell death through mitochondrial enzyme activation as compared to 10 % FBS. Apoptotic cell death was observed by chromosome condensation and the increase of sub-G0/G1 population. Serum deprivation reduced cell growth rate, which was confirmed by the decrease of S-phase population in cell cycle. Serum deprivation significantly increased caspase-9 activity and cytochrome c release from mitochondria into cytosol. Serum deprivation-induced mitochondrial changes were also indicated by the increase of ROS production and the activation of mitochondrial enzyme, succinate dehydrogenase. Mitochondrial enzyme activity increased by serum deprivation was reduced by the treatment with rotenone, mitochondrial electron transport inhibitor. In conclusion, serum deprivation induced mitochondrial apoptotic cell death through the elevation of mitochondrial changes such as ROS production, cytochrome c release and caspase-9 activation. It suggests that drug sensitivity could be enhanced by the increase of mitochondrial enzyme activity in serum-deprived condition.

• 한국식품과학회지
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• 제13권3호
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• pp.188-193
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• 1981

Potassium biphthalate buffer와 쌀, 버섯, 쇠고기에서의 pantothenic acid 열분해속도(熱分解速度)에 미치는 온도(溫度)와 pH의 영향(影響)을 검토하였다. 완충액시료와 식품시료에서의 pantothenic acid 열분해반응(熱分解反應)은 $60{\sim}140^{\circ}C$에서 1차(次) 반응(反應)을 나타내었다. 또한 Arrhenius식(式)으로부터 구한 활성화에너지(Ea)는 $15,700{\sim}17,300\;cal/mole$이었다. 식품시료와 완충액시료의 $D_{120}$을 비교해 본 결과 식품시료가 약 18시간(時間)으로 완충액시료의 15.4시간(時間)보다 높은 것으로 식품시료가 열(熱)에 보다 안정함을 나타내었다. 식품시료와 완충액시료가 모두 $p{\geq}6.46$인 경우에 pH가 증가함에 따라 반응속도상수(反應速度常數)는 증가하였으며 Ea는 감소하였다. 이 실험 결과를 바탕으로 두 pH 범위에서 반응속도상수(反應速度常數)의 온도(溫度) 및 pH 변화에 따론 예측(豫測)모형(模型)을 설정하였다.

• Nuclear Engineering and Technology
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• 제5권4호
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• pp.339-343
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• 1973

• Animal Bioscience
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• 제35권3호
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• pp.399-409
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• 2022

Objective: Follicle-stimulating hormone (FSH) is the central hormone involved in mammalian reproduction, maturation at puberty, and gamete production that mediates its function by control of follicle growth and function. The present study investigated the mutations involved in the regulation of FSH receptor (FSHR) activation. Methods: We analyzed seven naturally-occurring mutations that were previously reported in human FSHR (hFSHR), in the context of equine FSHR (eFSHR); these include one constitutively activation variant, one allelic variant, and five inactivating variants. These mutations were introduced into wild-type eFSHR (eFSHR-wt) sequence to generate mutants that were designated as eFSHR-D566G, -A306T, -A189V, -N191I, -R572C, -A574V, and -R633H. Mutants were transfected into PathHunter EA-parental CHO-K1 cells expressing β-arrestin. The biological function of mutants was analyzed by quantitating cAMP accumulation in cells incubated with increasing concentrations of FSH. Results: Cells expressing eFSHR-D566G exhibited an 8.6-fold increase in basal cAMP response, as compared to that in eFSHR-wt. The allelic variation mutant eFSHR-A306T was not found to affect the basal cAMP response or half maximal effective concentration (EC₅₀) levels. On the other hand, eFSHR-D566G and eFSHR-A306T displayed a 1.5- and 1.4-fold increase in the maximal response, respectively. Signal transduction was found to be completely impaired in case of the inactivating mutants eFSHR-A189V, -R572C, and -A574V. When compared with eFSHR-wt, eFSHR-N191I displayed a 5.4-fold decrease in the EC₅₀ levels (3,910 ng/mL) and a 2.3-fold decrease in the maximal response. In contrast, cells expressing eFSHR-R633H displayed in a similar manner to that of the cells expressing the eFSHR-wt on signal transduction and maximal response. Conclusion: The activating mutant eFSHR-D566G greatly enhanced the signal transduction in response to FSH, in the absence of agonist treatment. We suggest that the state of activation of the eFSHR can modulate its basal cAMP accumulation.