• Bulletin of the Korean Chemical Society
• /
• 제11권1호
• /
• pp.49-54
• /
• 1990

The gas-phase thermolysis reactions of ${\alpha}$- and ${\beta}$-methylated ethyl formates, Y = $CH-X-CHR_1CH_2R_2$ where X = Y = O or S and $R_1\;=\;R_2$ = H or $CH_3$, are investigated theoretically using the AM1 method. The experimental reactivity order is reproduced correctly by AM1 in all cases. The thermolysis proceeds through a six-membered cyclic transition state conforming to a retro-ene reaction, which can be conveniently interpreted using the frontier orbital theory of three-species interactions. The methyl group substituted at $C_{\alpha}\;or\;C_{\beta}$ is shown to elevate the ${\pi}$-HOMO of the donor fragment (Y = C) and depress the ${\sigma}^{\ast}$-LUMO of the acceptor fragment ($C_{\beta}$-H), increasing the nucleophilicity of Y toward ${\beta}$-hydrogen which in turn increases the reactivity. The two bond breaking processes of the $C_{\alpha}$-X and $C_{\beta}$-H bonds are concerted but not synchronous so that the reaction takes place in two stages as Taylor suggested. The initial cleavage of $C_{\alpha}$-X is of little importance but the subsequent scission of $C_{\beta}$-H occurs in a rate determining stage.

• Psychiatry investigation
• /
• 제15권12호
• /
• pp.1121-1129
• /
• 2018

Objective Categorical syndrome such as schizophrenia could be the complex of many continuous mental structure phenotypes including several personality development/degeneration dimensions. This is the study to search heritability and familiality of MMPI personality dimensions in the Korean schizophrenic LD (Linkage Disequilibrium) families. Methods We have recruited 204 probands (with schizophrenia) with their parents and siblings whenever possible. We have used MMPI questionnaires for measuring personality and symptomatic dimensions. Heritabilities of personality dimensions in total 543 family members were estimated using Sequential Oligogenic Linkage Analysis Routines (SOLAR). Personality dimensions in total family members were compared with those in 307 healthy unrelated controls for measuring the familialities using ANOVA analysis. Results Seven of the 10 MMPI variables were significantly heritable and were included in the subsequent analyses. The three groups (control, unaffected 1st degree relative, case) were found to be significantly different with the expected order of average group scores for all heritable dimensions. Conclusion Our results show that the aberrations in several personality dimensions could form the complexity of schizophrenic syndrome as a result of genetic-environment coactions or interactions in spite of some limitations (recruited family, phenotyping).

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

• BMB Reports
• /
• 제34권6호
• /
• pp.537-543
• /
• 2001

In the present study, an in vitro ELISA system to assess the interaction between Src homology (SH)2 domains and phosphotyrosine that contain peptides was established using purified GST-conjugated SH2 proteins and synthetic biotinylated phosphotyrosine that contain oligopeptides. The SH2 domains bound the relevant phosphopeptides that were immobilized in the streptavidin-coated microtiter plate in a highly specific and dose-dependent manner. The epidermal growth factor receptor (EGFR)-, T antigen (T Ag)-, and platelet-derived growth factor receptor (PDGFR)-derived phosphopeptides interacted with the growth factor receptor binding protein (Grb)2/SH2, Lck/SH2, and phosphatidyl inositol 3-kinase (PI3K) p85/SH2, respectively. No cross-reactions were observed. Competitive inhibition experiments showed that a short phosphopeptide of only four amino acids was long enough to determine the binding specificity. Optimal concentrations of the GST-SH2 fusion protein and phosphopeptide in this new ELISA system for screening the binding blockers were chosen at 2nM and 500nM, respectively. When two candidate compounds were tested in our ELISA system, they specifically inhibited the Lck/SH2 and/or p85/SH2 binding to the relevant phosphopeptides. Our results indicate that this ELISA system could be used as an easy screening method for the discovery of specific binding blockers of protein-protein interactions via SH2 domains.

• Journal of Ginseng Research
• /
• 제45권6호
• /
• pp.642-653
• /
• 2021

Background: Effective strategies are dramatically needed to prevent and improve the recovery from myocardial ischemia and reperfusion (I/R) injury. Direct interactions between the mitochondria and endoplasmic reticulum (ER) during heart diseases have been recently investigated. This study was designed to explore the cardioprotective effects of gypenoside XVII (GP-17) against I/R injury. The roles of ER stress, mitochondrial injury, and their crosstalk within I/R injury and in GP-17einduced cardioprotection are also explored. Methods: Cardiac contractility function was recorded in Langendorff-perfused rat hearts. The effects of GP-17 on mitochondrial function including mitochondrial permeability transition pore opening, reactive oxygen species production, and respiratory function were determined using fluorescence detection kits on mitochondria isolated from the rat hearts. H9c2 cardiomyocytes were used to explore the effects of GP-17 on hypoxia/reoxygenation. Results: We found that GP-17 inhibits myocardial apoptosis, reduces cardiac dysfunction, and improves contractile recovery in rat hearts. Our results also demonstrate that apoptosis induced by I/R is predominantly mediated by ER stress and associated with mitochondrial injury. Moreover, the cardioprotective effects of GP-17 are controlled by the PI3K/AKT and P38 signaling pathways. Conclusion: GP-17 inhibits I/R-induced mitochondrial injury by delaying the onset of ER stress through the PI3K/AKT and P38 signaling pathways.

• 대한원격탐사학회지
• /
• 제29권3호
• /
• pp.275-291
• /
• 2013

Monitoring the global Gross Primary Pproduction (GPP) is relevant to understanding the global carbon cycle and evaluating the effects of interannual climate variation on food and fiber production. GPP, the flux of carbon into ecosystems via photosynthetic assimilation, is an important variable in the global carbon cycle and a key process in land surface-atmosphere interactions. The Moderate-resolution Imaging Spectroradiometer (MODIS) is one of the primary global monitoring sensors. MODIS GPP has some of the problems that have been proven in several studies. Therefore this study was to solve the regional mismatch that occurs when using the MODIS GPP global product over Korea. To solve this problem, we estimated each of the GPP component variables separately to improve the GPP estimates. We compared our GPP estimates with validation GPP data to assess their accuracy. For all sites, the correlation was close with high significance ($R^2=0.8164$, $RMSE=0.6126g{\cdot}C{\cdot}m^{-2}{\cdot}d^{-1}$, $bias=-0.0271g{\cdot}C{\cdot}m^{-2}{\cdot}d^{-1}$). We also compared our results to those of other models. The component variables tended to be either over- or under-estimated when compared to those in other studies over the Korean peninsula, although the estimated GPP was better. The results of this study will likely improve carbon cycle modeling by capturing finer patterns with an integrated method of remote sensing.

• Journal of Microbiology and Biotechnology
• /
• 제28권9호
• /
• pp.1482-1492
• /
• 2018

Fusarium oxysporum trypsin (FOT) is a fungal serine protease similar to mammal trypsin. The FOT could be successfully expressed in Pichiapastoris by engineering the natural propeptide APQEIPN. In this study, we constructed two recombinant enzymes with engineered amino acid sequences added to the N-terminus of FOT and expressed in P. pastoris. The N-terminal residues had various effects on the structural and functional properties of trypsin. The FOT, and the recombinants TE (with peptide YVEF) and TS (with peptide YV) displayed the same optimum temperature ($40^{\circ}C$) and pH (8.0). However, the combinants TE and TS showed significantly increased thermal stability at $40^{\circ}C$ and $50^{\circ}C$. Moreover, the combinants TE and TS also showed enhanced tolerance of alkaline pH conditions. Compared with those of wild-type FOT, the intramolecular hydrogen bonds and the cation ${\pi}$-interactions of the recombinants TE and TS were significantly increased. The recombinants TE and TS also had significantly increased catalytic efficiencies (referring to the specificity constant, $k_{cat}/K_m$), 1.75-fold and 1.23-fold than wild-type FOT. In silico modeling analysis uncovered that the introduction of the peptides YVEF and YV resulted in shorter distances between the substrate binding pocket (D174, G198, and G208) and catalytic triad (His42, Asp102, and Ser180), which would improve the electron transfer rate and catalytic efficiency. In addition, N-terminal residues modification described here may be a useful approach for improving the catalytic efficiencies and characteristics of other target enzymes.

• 디지털융복합연구
• /
• 제12권6호
• /
• pp.587-595
• /
• 2014

최근 SNS(Social Network Service) 및 스마트기기의 이용자가 급속히 증가하고 있는 시점에서 SNS를 교육에 활용하기 위한 다양한 교수학습 모형 및 교수 방법에 대한 연구가 진행되고 있다. 대학 교육에서 학습 환경으로서의 소셜미디어를 고찰하고 학업성취도와의 관계를 실증적으로 분석한 연구는 미비하다. 창의인재 양성을 위해 여러 종류의 학습경험이 요구되는 시점에서 SNS를 활용한 정보 공유, 토론, 정보교환이 필요하다. 대학의 교양 컴퓨터 교육에 SNS를 활용하면 학습자들의 생각과 의견을 보다 다양하고 효과적으로 파악이 가능하다. SNS를 통하여 각자 개인적인 공간에서 학습자와 교수자간 혹은 학습자와 학습자간 활동과 관련된 정보를 공유하고 의견을 나누는 활동을 함으로써 실시간으로 피드백을 줄 수 있어서 학습자의 컴퓨터를 활용하는 능력이 향상될 수가 있다. 특히 학습이 부진한 학생들에게 SNS를 이용하여 실시간으로 문제를 해결 할 수 있도록 도움을 줄 수 있어서 학업성취도 향상 기회를 제공할 수가 있다.

• 대한화학회지
• /
• 제34권4호
• /
• pp.331-339
• /
• 1990

cis-diamminedichloroplatinum (II)에서 아민리간드가 변화할 때, 항암성과 백금원자의 전자구조 사이의 관계를 연구하였고, 또 이러한 착물과 DNA base인 1-methylcytosine의 상호작용에 대한 메카니즘을 알기 위해서 백금(II)착물들을 분자궤도함수론적으로 연구하였다. 그 결과, 백금착물에서 중심금속의 atomic charge가 항암성에 영향을 미치고 있음을 알았다. 또한 백금착물과 1-methylcytosine의 결합은 리간드에서 금속원자로 전하이동을 하였고, 이 때 Pt(II)의 6p-orbital이 중요한 하고 있음을 발견한다. Pt-N3결합성은 $\alpha$ 와 $\pi$ 성분을 포함하고 있으며, 실험한 값과 비교할 때 비교할 때 항암성이 큰 백금착물일수록 Pt-N3 결합이 강하게 형성하고 있었다.

• Bulletin of the Korean Chemical Society
• /
• 제35권12호
• /
• pp.3590-3594
• /
• 2014

Blue phosphorescent $(dfpypy)_2Ir(mppy)$, where dfpypy = 2',6'-difluoro-2,3'-bipyridine and mppy = 5-methyl-2-phenylpyridine, has been synthesized by newly developed effective method and its solid state structure and photoluminescent properties are investigated. The glass-transition and decomposition temperature of the compound appear at $160^{\circ}C$ and $360^{\circ}C$, respectively. In a crystal packing structure, there are two kinds of intermolecular interactions such as hydrogen bonding ($C-H{\cdots}F$) and edge-to-face $C-H{\cdots}{\pi}(py)$ interaction. This compound emits bright blue phosphorescence with ${\lambda}_{max}=472nm$ and quantum efficiencies of 0.23 and 0.32 in fluid and the solid state. The emission band of the compound is red-shifted by 40 nm relative to homoleptic congener, $Ir(dfpypy)_3$. The ancillary ligand in $(dfpypy)_2Ir(mppy)$ has been found to significantly destabilize HOMO energy, compared to $Ir(dfpypy)_3$, $(dfpypy)_2Ir(acac)$ and $(dfpypy)_2Ir(dpm)$, without significantly changing LUMO energy.