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Catalytic Reactivity of Transition Metal (Pd, Ni) complexes with Aminophosphines; I. Carbon-Carbon coupling reactions (Aminophosphine류가 배위된 전이금속(Pd, Ni) 착물의 촉매반응; I. 탄소-탄소 짝지움 반응)

  • Jung, Maeng-Joon;Lee, Chul-Jae;Kim, Dong-Yeub
    • Journal of the Korean Society of Industry Convergence
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    • v.7 no.1
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    • pp.107-113
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    • 2004
  • Several transition metal complexes, [$M(L)X_2$](M=Pd(II), Ni(II); X=CI, Br) are prepared with aminophosphine ligands such as 1,2-bis{(diphenylphosphino)amino}ethane{$Ph_2PNHCH_2CH_2NHPPh_2$}($L_1$), 1,2-bis{(diphenylphosphino)amino}propane{$Ph_2PNHCH(CH_3)CH_2NHPPh_2$}($L_2$), trans-1,2-bis{(diphenylphosphino)amino}cyclohexane{$Ph_2PNHC_6H_{10}NHPPh_2$}($L_3$) and 1,2-bis{(diphenylphosphino)amino}benzene{$Ph_2PNHC_6H_4NHPPh_2$}($L_4$). The properties of these complexes are characterized by optical spectroscopic methods including UV/vis spectroscopy, CD, IR, $^1H$- and $^{31}P-NMR$ together with conductometer and elemental analysis. All complexes are stable under atmospheric environment. Catalytic reactivity for C-C coupling between [$M(L)X_2$] and Grignard reagents(RMgX; R=phenyl, propyl, buthyl) by thermolysis were investigated utilizing GC/mass, $^1H$- and $^{13}C-NMR$. When mol scale is 1:20 at [$Pd(L)Cl_2$] and Grignard reagents, the high catalytic activity for C-C coupling is apparent. The [$M(L)X_2$](X=Cl, Br) complexes which have strong bond at M-P exhibit high yields for C-C coupling reactions. When the central metal ion is Pd(II), the high catalytic activity for C-C coupling is apparent. The complex coordinated with Br shows higher catalytic activity for C-C coupling reactions compared to Cl.

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Nickel Complexes Having (N-C-N) Tridentate Ligands ((N-C-N) 세자리 리간드를 가지는 니켈 착물)

  • Lee, Dong-Hwan;Park, Soon-Heum
    • Journal of the Korean Chemical Society
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    • v.51 no.6
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    • pp.499-505
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    • 2007
  • Monomeric complexes of nickel(II) having terdentate bis(imino)aryl ligands (N,C,N-pincer) are reported. New complexes (2,6-(ArN=CH)2C6H3)NiBr (Ar=2,6-dimethylphenyl (1), 2,6-diisopropylphenyl (2)) have been synthesized through oxidative addition of 1,3-(ArN=CH)2C6H3Br (bis(N-Ar)-2-bromoisophthalaldimine: Ar=Ph-2,6-Me2, Ph-2,6-iPr2) to Ni(COD)2 (COD=1,5-cyclooctadiene), in high yields. The development of a synthetic route to ligands and nickel complexes is outlined. The complexes were characterized by IR, 1H-NMR and elemental analysis. Full characterization of complexes 1 and 2 is discussed. An investigation into the catalytic activity of the complexes in ethylene polymerization was performed, resulting in no formation of polyethylenes but producing a small amount of oily oligomers. Preliminary results indicate that the pincer complexes were found to be inactive as catalysts in ethylene polymerization.

Regulation of AKT Activity by Inhibition of the Pleckstrin Homology Domain-PtdIns(3,4,5)P3 Interaction Using Flavonoids

  • Kang, Yerin;Jang, Geupil;Ahn, Seunghyun;Lee, Youngshim;Shin, Soon Young;Yoon, Youngdae
    • Journal of Microbiology and Biotechnology
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    • v.28 no.8
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    • pp.1401-1411
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    • 2018
  • The serine-threonine kinase AKT plays a pivotal role in tumor progression and is frequently overactivated in cancer cells; this protein is therefore a critical therapeutic target for cancer intervention. We aimed to identify small molecule inhibitors of the pleckstrin homology (PH) domain of AKT to disrupt binding of phosphatidylinositol-3,4,5-trisphosphate (PIP3), thereby downregulating AKT activity. Liposome pulldown assays coupled with fluorescence spectrometry were used to screen flavonoids for inhibition of the AKT PH-PIP3 interaction. Western blotting was used to determine the effects of the inhibitors on AKT activation in cancer cells, and in silico docking was used for structural analysis and optimization of inhibitor structure. Several flavonoids showing up to 50% inhibition of the AKT PH-PIP3 interaction decreased the level of AKT activation at the cellular level. In addition, the modified flavonoid showed increased inhibitory effects and the approach would be applied to develop anticancer drug candidates. In this study, we provide a rationale for targeting the lipid-binding domain of AKT, rather than the catalytic kinase domain, in anticancer drug development.

Oxyradical Formation during the Hepatocarcinogenesis in Rat (흰쥐 간발암화 과정에서의 산소유리기의 동태)

  • Kim, Hyoung-Chun;Chun, Wan-Jhoo;Lee, Hyun-Woo;Kwon, Myung-Sang;Song, Kye-Yong;Jhoo, Wang-Kee
    • YAKHAK HOEJI
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    • v.36 no.2
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    • pp.180-187
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    • 1992
  • This study investigated the hypothesis that carcinogen-induced elevation of oxyradical during the hepatocarcinogenesis in rat. The hepatic preneoplastic lesions in the Spraque-Dawley rats were induced by the carcinogen treatment such as diethylnitrosamine(DEN) and acetylaminofluorene(AAF) in combination with partial hepatectomy(PH). The liver sample was taken at 2, 6, 10 and 16 months after carcinogen treatments followed by PH. Carcinogen treatments initially increased the indices of oxidative damage(activities of xanthine oxidase and production rates of superoxide anion, microsomal hydrogen peroxide, hydroxyl radical) in the liver compared to PH groups. However, cytosolic hydrogen peroxide did not change significantly throughout the full time period. Of hydrogen peroxide scavenger, the catalase was remained lower than PH groups, whereas the peroxidase was increased after carcinogen treatments. Morphologically, the immunohistochemical analysis with glutathione-S-transferase of a placenta form(GSTP) antibody was used to detect the induction of preneoplastic nodules. During the hepatocarcinogenesis, both production rate of hydroxyl radical and activity of glutathione-S-transferase(GST) markedly increased with the appearance of the preneoplastic nodule. These results indicated that the hydroxyl radical of reactive oxygen species seemed to have a major influence on the hepatocarcinogenesis and the effect of time after removal of the carcinogen also appeared to be highly critical in the hepatocarcinogenesis.

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Ionic Equilibria of Pt(IV), Pd(II) and Rh(III) in Hydrochloric Acid Solution (염산용액(鹽酸溶液)에서 白金(IV), 팔라듐(II)과 로듐(III)의 이온평형(平衡))

  • Lee, Man-Seung;Lee, Jin-Young
    • Resources Recycling
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    • v.18 no.1
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    • pp.30-37
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    • 2009
  • Distribution diagram of Pt(IV), Pd(II), and Rh(III) in HCl solution was obtained as a function of HCl concentration from 0.001 to 10 M by considering complex formation reaction together with mass balance. When HCl concentration was higher than 0.1 M, most of Pt and Pd in HCl solution exist as $PtCl_6^{2-}$ and $PtCl_4^{2-}$. The concentration of HCl had a feat effect on the speciation of Rh(III). As HCl concentration increases from 0.1 to 10 M, the pedominant species changes from $PhCl_5^{2-}$ to $PhCl_6^{3-}$. Interaction parameters of $PtCl_6^{2-}$ and $PdCl_4^{2-}$ with hydrogen ion were evaluated from the solvent extraction data of Pt and Pd reported in the literature.

Two-zone 확산법을 이용한 다결정 실리콘 박막으로의 Phosphorus 도핑에 관한 연구

  • 황민욱;김윤해;이석규;엄명윤;박영욱;김형준
    • Proceedings of the Korean Vacuum Society Conference
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    • 2000.02a
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    • pp.81-81
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    • 2000
  • 본 연구는 고집적 반도체 소자의 제조 공정에 있어서 산화막을 형성하지 않고 굴곡진 표면을 균일하게 고농도로 도핑하기 위한 방안의 일환으로 기존의 PH3 대신 고체 P를 직접 이용한 2-zone 확산법으로 다결정 Si에 도핑하는 방법을 채택하고, 그 rksmdtjddmdf 검토하는데 목적이 있다. 도핑 시간에 따른 확산 경향을 살펴본 결과, 시간이 증가함에 따라 도핑이 증가하는 뚜렷한 경향을 나타내었으며, 온도가 증가할수록 시간에 따른 농도의 증가량이 커지는 것을 알 수 있었다. 따라서, 고온에 비해 저온에서 더 빨리 pile-up이 일어나며 표면 부근의 농도가 포화상태에 빨리도달하는 것을 알 수 있었다. 다결정 Si에서의 확산거동을 살펴본 결과, 결정립 크기가 적을수록 저항이 높게 나타났으며, 단결정 Si의 저항값보다 약 4~5배 가까이 높은 값을 나타내었다. 또한 동일한 온도에서 시간에 따라 표면 부근의 pile-up 현상이 증가하는 뚜렷한 경향을 보여 주었다. 온도가 감소할수록 pili-up 현상이 증가하는 경향을 나타내었으며, 입계를 통한 빠른 확산에 의해 단결정 Si에 비해 표면 pile-up의 포화가 늦게 일어나는 것을 알 수 있었다. 고체 P를 source로 사용한 경우와 PH3 (phosphine)을 source로 사용한 경우를 비교 분석한 결과, 75$0^{\circ}C$에서 PH3에 비해 고체 P를 사용한 경우의 표면농도가 약 50배 정도로 높게 도핑된 것을 알 수 있었다. 도핑된 P중에서 전기적으로 활성화되어 있는 성분을 알아본 결과, SIMS의 결과와 유사하게 고체 P의 경우가 약 50배 높은 값을 나타내었다. 실제 소자의 특성을 알아보기 위하여 커패시터를 제작하여 측정하여 본 결과, 추가의 도핑을 하지 않은 시편에 비해 고체 P를 도핑한 시편이 약 8%의 Cmin 값의 증가를 보였으며, PH3에 비해 약 3%의 증가된 값을 나타냈었다. 누설전류 특성은 2V에서 수 fA/$\mu\textrm{m}$2로 양호하게 나타났다. 실험 결과 고체 P를 이용한 경우 더 우수한 특성을 나타내었으나, 예상과는 달리 차이가 적게 나타났다. 그 원인은 소자 제조 공정에서 콘택 부분에 큰 저항 성분이 형성되어 생긴 문제로 생각된다. 또한 실험에 사용된 유전체의 두께가 두꺼워 HSG 사이의 갭 부분이 캐패시턴스 증가에 기여를 충분히 못한 것으로 사료된다. 따라서, 제조 공정 상의 문제점을 제거하고 고체 P를 사용할 경우 본 실험에 비해 보다 증진된 특성을 보여줄 것으로 기대된다. 이상의 결론을 토대로 볼 때, 2-zone 확산법을 이용한 P 도핑 방법은 저온에서 효과적으로 다결정 Si에 고농도의 도핑을 할 수 있다고 생각된다.

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Effects of growth interruption on the photoluminescence characteristics of InGaAs/InP quantum wells (성장정지효과에 의한 InGaAs/InP 양자우물구조의 Photoluminescence 특성 변화)

  • 문영부;이태완;김대연;윤의준;유지범
    • Journal of the Korean Vacuum Society
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    • v.7 no.2
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    • pp.104-111
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    • 1998
  • The InGaAs/InP quantum wells(QWs) were grown by low pressure metalorganic chemical vapor deposition and the effects of growth interruption steps on their interfacial structures were investigated by measuring photoluminescence spectra. When InP or InGaAs surface was treated under the same group V ambient, the full width at half maximum (FWHM) of the QW peak increased possibly due to the incorporation of impurities during the growth interruption time. When InP surface was treated under $AsH_3$, howerer, the PL peak showed red-shift due to the As-P exchange reaction and the change of FWHM was not remarkable. The effective thickness of InAs interfacial layer formed during $AsH_3$, treatment on the InP surface was calculated to be 1~2 monolayers. In the case of InGaAs treatment under $PH_3$, the PL peak energy and the FWHM increasied. This results suggest that $PH_3$ treatment on the InGaAs surface suppresses the incorporation of As into the subsequent InP layer and the local replacement of As by P occurs simultaneously.

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Fumigant Activity of Phosphine Against Three Wood Boring Beetles, Platypus koryoensis, Cryphalus fulvus, and Xyleborus mutilatus (광릉긴나무좀, 왕녹나무좀, 노랑애나무좀 성충에 대한 포스핀의 훈증활성)

  • Cho, Sung Woo;Kim, Sung Il;Kim, Hyun Kyung;Kim, Gil-Hah
    • Korean journal of applied entomology
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    • v.58 no.1
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    • pp.31-35
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    • 2019
  • Many forest pests have caused problems for wood quarantine. The fumigation activity of phosphine ($PH_3$) was examined for the adults of three wood-boring insect pests. The $LCT_{99}$ values for Platypus koryoensis, Cryphalus fulvus, and Xyleborus mutilates were 3.192, 0.994, and $0.501mg{\cdot}h/L$ at $20^{\circ}C$, respectively. The effectiveness of $PH_3$ was increasingly time dependent for all doses tested in all three species. In particular, P. koryoensis showed 100% mortality at doses higher than 0.4 mg/L 7 days after fumigation. These results indicate that methyl bromide could be substituted for $PH_3$ for adults of these three species of wood pest.

What Determines Open Innovation in SMEs? An Empirical Study Considering the Strategy-Culture Mixed Typology and Environmental Dynamism (무엇이 중소기업의 개방형 혁신을 결정하는가? 전략-문화 혼합유형과 환경 역동성을 고려한 실증연구)

  • Kwon, Se-In;Yang, Jong-Gon
    • Journal of Convergence for Information Technology
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    • v.12 no.4
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    • pp.345-353
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    • 2022
  • The purpose of this study is to identify the types for open innovation of SMEs considering strategic- culture mixed typology and environmental dynamism. The analysis results of 182 SMEs classified into 4 groups are as follows. First, type PD had a positive effect on innovation performance in both in-bound and out-bound innovation and had improved performance through in-bound innovation in a dynamic technical environment. While DH had no significant effect on both innovations. Second, PH and DD, strategy-culture mismatched types, had a single effect of innovation that affected performance. No moderating effects of environmental dynamism had been shown in types PH, DD, DH. SMEs that aim for open innovation should strive to improve performance by aligning change-oriented strategy with creative and challenging culture.

Ahnak depletion accelerates liver regeneration by modulating the TGF-β/Smad signaling pathway

  • Yang, Insook;Son, Yeri;Shin, Jae Hoon;Kim, Il Yong;Seong, Je Kyung
    • BMB Reports
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    • v.55 no.8
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    • pp.401-406
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    • 2022
  • Ahnak, a large protein first identified as an inhibitor of TGF-β signaling in human neuroblastoma, was recently shown to promote TGF-β in some cancers. The TGF-β signaling pathway regulates cell growth, various biological functions, and cancer growth and metastasis. In this study, we used Ahnak knockout (KO) mice that underwent a 70% partial hepatectomy (PH) to investigate the function of Ahnak in TGF-β signaling during liver regeneration. At the indicated time points after PH, we analyzed the mRNA and protein expression of the TGF -β/Smad signaling pathway and cell cycle-related factors, evaluated the cell cycle through proliferating cell nuclear antigen (PCNA) immunostaining, analyzed the mitotic index by hematoxylin and eosin staining. We also measured the ratio of liver tissue weight to body weight. Activation of TGF-β signaling was confirmed by analyzing the levels of phospho-Smad 2 and 3 in the liver at the indicated time points after PH and was lower in Ahnak KO mice than in WT mice. The expression levels of cyclin B1, D1, and E1; proteins in the Rb/E2F transcriptional pathway, which regulates the cell cycle; and the numbers of PCNA-positive cells were increased in Ahnak KO mice and showed tendencies opposite that of TGF-β expression. During postoperative regeneration, the liver weight to body weight ratio tended to increase faster in Ahnak KO mice. However, 7 days after PH, both groups of mice showed similar rates of regeneration, following which their active regeneration stopped. Analysis of hepatocytes undergoing mitosis showed that there were more mitotic cells in Ahnak KO mice, consistent with the weight ratio. Our findings suggest that Ahnak enhances TGF-β signaling during postoperative liver regeneration, resulting in cell cycle disruption; this highlights a novel role of Ahnak in liver regeneration. These results provide new insight into liver regeneration and potential treatment targets for liver diseases that require surgical treatment.