• 제목/요약/키워드: $S_N1$ mechanism

검색결과 717건 처리시간 0.029초

경정립 미세화에 따른 이상조직 탄소강의 하중에 따른 마멸기구 (Sliding Wear Mechanism of Ultra-Fine Grained Low Carbon Dual Phase Steel as a Function of Applied Load)

  • 유현석;이슬기;신동혁;김용석
    • 소성∙가공
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    • 제16권4호
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    • pp.299-303
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    • 2007
  • Dry sliding wear behavior of ultra-fine grained(UFG) plain low carbon dual phase steel, of which microstructure consists of hard martensite in a ductile ferrite matrix, has been investigated. The wear characteristics of the UFG dual phase steel was compared with that of a coarse grained dual phase steel under various applied load conditions. Dry sliding wear test were carried out using a pin-on-disk type tester at various loads of 1N to 100N under a constant sliding speed condition of 0.20m/s against an AISI 52100 bearing steel ball at room temperature. The sliding distance was fixed as 1000m for all wear tests. The wear rate was calculated by dividing the weight loss, measured to the accuracy of 10-5g by the specific gravity and sliding distance. The worn surfaces and wear debris were analyzed by SEM, EDS and profilometer. Micro-vickers hardness of the cross section of worn surfaces were conducted to analyze strain hardening underneath the contact surfaces. The wear mechanism of the UFG dual phase steel was investigated with emphasis on the unstable nature of the grain boundaries of the UFG microstructure.

신생 백서의 저산소 허혈 뇌손상에서 Transforming Growth Factor-β1 투여에 따른 Nitric Oxide Synthase 이성체와 N-methyl-D-aspartate 수용체 아단위의 발현 (Expression of nitric oxide synthase isoforms and N-methyl-D-aspartate receptor subunits according to transforming growth factor-β1 administration after hypoxic-ischemic brain injury in neonatal rats)

  • 고혜영;서억수;김우택
    • Clinical and Experimental Pediatrics
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    • 제52권5호
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    • pp.594-602
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    • 2009
  • 목 적 : $TGF-{\beta}1$는 흥분독성을 억제시키고 질소 산화물 생성 억제를 통한 신경세포 보호 효과가 있다고 알려져 있지만 주산기저산소 허혈 뇌손상에서 그 기전은 아직도 확실히 밝혀져 있지 않고 있다. 따라서 이번 연구에서는 신생 백서의 저산소 허혈 뇌손상에서 산화질소로 인한 신경독성 및 글루탐산염에 의한 흥분독성과 $TGF-{\beta}1$의 관계를 보고자 하였다. 방 법 : 생체외 실험으로 재태 기간 19일된 태아 백서의 대뇌피질 세포를 배양하여 1% O2 배양기에서 저산소 상태로 뇌세포손상을 유도하여 저산소군(Hypoxia), 저산소 손상 30분 전 $TGF-{\beta}1$ (1, 5, 10 ng/mL) 투여군(H+$TGF-{\beta}1$)으로 나누어 정상 산소군 (Control)과 비교하였다. 생체 내 실험은 생후 7일된 백서의 좌측 총 경동맥을 결찰한 후 저산소 (7.5% O2) 상태로 2시간 노출시켜서, 저산소 허혈 뇌손상을 유발하였다. 아무런 처치도 하지 않은 정상 대조군(Control), 경동맥 노출 후 봉합 시술만 시행한 정상 Sham 수술군(Sham-OP), 손상 30분 전 생리식염수를 주입 후 경동맥 결찰과 저산소 노출을 시행한 저산소 허혈 대조군(HI+ Vehicle), 손상 30분 전 $TGF-{\beta}1$을 대뇌로 투여하고 경동맥 결찰과 저산소 노출을 시행한 저산소 허혈 $TGF-{\beta}1$ 투여군(HI+$TGF-{\beta}1$)으로 나누어 비교분석하였다. 흥분독성과의 관련을 알아보기 위하여 NMDA 수용체 아단위를 이용하였고, 질소산화물과의 관련을 알아보기 위해 iNOS, eNOS 및 nNOS를 이용하여 western blotting과 실시간 중합효소연쇄반응을 하였다. 결 과 : 생체 외 실험에서 iNOS의 발현은 정상 산소군과 저산소군 간에 차이가 없었으며, $TGF-{\beta}1$ 투여군에서는 발현이 증가하였으며 이는 농도와는 상관성이 없었다. eNOS, nNOS의 발현은 1 ng/mL의 $TGF-{\beta}1$ 투여군에서 저산소군보다 감소하였다. 생체 내 실험에서는 iNOS와 iNOS mRNA의 발현은 $TGF-{\beta}1$ 투여한 후 저산소 대조군보다 증가하였다. eNOS와 nNOS 발현은 정상 대조군 보다 저산소 대조군에서 감소하였고, eNOS의 발현은 $TGF-{\beta}1$ 투여군에서 증가하였지만 nNOS의 발현은 증가하지 않아 통계적 유의성이 없었다. eNOS mRNA와 nNOS mRNA의 발현은 iNOS와 반대로 $TGF-{\beta}1$ 투여군에서 저산소 대조군보다 감소하였다. NMDA 수용체 아단위 mRNA의 발현은 정상 대조군과 Sham 수술군에 비해 저산소 대조군에서 모두 감소하였으나 $TGF-{\beta}1$ 투여군에서 NR2C를 제외한 나머지 아단위의 발현은 저산소 대조군보다 증가하였다. 결 론 : 신생백서의 저산소 허혈 뇌손상에서 $TGF-{\beta}1$ 치료군에서 저산소로 인하여 감소된 NMDA 수용체 아단위의 발현을 증가시켜 흥분독성 기전과 관련성을 보이며, 증가된 iNOS 발현을 감소시키고 감소된 eNOS 발현을 증가시키는 질소 산화물 중재를 통한 뇌 보호 작용에 연관이 있을 것으로 생각된다.

산 촉매하에서 cis-$[Co(en)_2(N_3)_2]^+$ 와 Fe(II) 와의 산화-환원반응에 대한 반응속도와 메카니즘 (Kinetics and Mechanism for Redox Reaction of cis-$[Co(en)_2(N_3)_2]^+$ with Fe(II) in Acidic Solution)

  • 박병각;김광진;임주상
    • 대한화학회지
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    • 제33권3호
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    • pp.309-314
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    • 1989
  • 산 용액내에서 cis-$[Co(en)_2(N_3)_2]^+$와 Fe(II)간의 산화-환원 반응속도를 UV/vis-분광광도계로 측정하였다. 여기서 촉매 $H^+$가 관여한 반응속도상수와 각 반응물의 반응차수 그리고 활성화파라메타를 구하여 이들 자료를 바탕으로 타당한 반응메카니즘을 제안하였다. 본 연구의 실험결과를 보면, Co(III)와 Fe(II) 그리고 $H^+$에 대해서 각각 1차로 총괄반응이 3차 반응이다. 이때 반응속도상수 $K_H^+$$3.27{\times}10^{-2}l^2{\cdot}mol^{-2}{\cdot}sec^{-1}$이였다. 그리고 활성화에너지 $E_a$는 14.8Kcal/mol, 활성화엔탈피 ${\Delta}H^{\neq}$는 14.2Kcal/mol, 활성화엔트로피 ${\Delta}S^{\neq}$는 -16.7e.u.였다. 이러한 실험적 사실을 바탕으로, 본 반응계에서 $H^+$가 촉매로 작용하여 내부권(inner-sphere) 메카니즘으로 산화-환원반응이 진행되는 타당한 반응메카니즘을 제안하였다.

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황의 친핵성 치환반응 (제11보). 염화나프탈렌술포닐과 아닐린과의 반응 (Nucleophilic Displacement at Sulfur Center (XI). Reaction of Naphthalenesulfonyl Chlorides with Anilines)

  • 이익춘;엄태섭;이억석
    • 대한화학회지
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    • 제22권5호
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    • pp.281-288
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    • 1978
  • 1-염화 및 2-염화나프탈렌술포닐과 아닐린과의 반응에서 그 반응의 유사 일차 반응속도상수($k_{obs}$)를 구하고 또한 2차 반응속도 상수 $k_2$및 3차반응 촉매속도상수 $k_3$$k_{obs}$로 부터 구하였다. 1-염화나프탈렌술포닐과의 반응에서는 Peri-hydrogen 효과가 관측되었다. 또한 Brensted 그림표에서는 큰 값의 ${\beta}$와 Hammett 그림표의 기울기로부터 크 음의 ${\rho}$값을 얻었다. 따라서 이 반응의 메카니즘은 매우 낮은 활성화파라미터의 값을 갖는 결과로$S_AN$반응메카니즘과 잘 일치되지만 associative$S_N2$메카니즘으로도 동일하게 잘 설명될 수 있었다.

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A possible mechanism responsible for translocation and secretion an alkaliphilic bacillus sp. S-1 pullulanase

  • Shim, Jae-Kyoung;Kim, Kyoung-Sook;Kim, Cheorl-Ho
    • Journal of Microbiology
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    • 제35권3호
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    • pp.213-221
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    • 1997
  • The secretion of the alkaliphilic Bacillus sp. S-1 extracellular pullulanase involves translocation across the cytoplasmic membrane of the Gram-positive bacterial cell envelope. Translocation of the intracellular pullulanase PUL-I, was traced to elucidate the mechanism and pathway of protein secretion from an alkaliphilic Bacillus sp. S-1. Pullulanase could be slowly bue quantitatively released into the medium during growth of the cells in medium contianing proteinase K. The released pullulanase lacked the N-terminal domain. The N-terminus is the sole membrane anchor in the pullulanase protein and was not affected by proteases, confirming that it is not exposed on the cell surface. Processing of a 180,000M$\_$r/ pullulanase to a 140,000M$\_$r/ polypeptide has been demonstrated in cell extracts using antibodies raised against 140,000M$\_$r/ extracellular form. Processing of the 180,000 M$\_$r/ protein occured during the preparation of extracts in an alkaline pH condition. A modified rapid extraction procedure suggested that the processing event also occured in vivo. Processing apparently increased the activity of pullulanase. The western blotting analysis with mouse anti-serum against 140-kDa extracellular pullulanase PUL-E showed that PUL-I is processed into PUL-X via intermediate form of PUL-E. Possible explanationa for the translocation are discussed.

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Kinetics and Mechanism of the Aminolysis of Anilino Thioethers with Benzylamines in Acetonitrile

  • Oh, Hyuck-Keun;Lee, Jae-Myun;Sung, Dae-Dong;Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • 제25권4호
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    • pp.557-559
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    • 2004
  • The aminolyses of anilinothioethers $(C_6H_5N(CH_3)CH_2SC_6H_4Z)$ in acetonitrile with benzylamines $(XC_6H_4CH_2NH_2)$ have been investigated. The rates are much lower in acetonitrile than in methanol (with aniline). The Bronsted ${\beta}_X$ values are similar but ${\beta}_Z$ values are smaller compared to those for the reactions in MeOH with anilines. The large negative ${\rho}_{XZ}({\cong}-0.8$, after correction for fall-off) value is interpreted to indicate a frontside attack $S_N2$ mechanism, in which the two oppositely changed reaction centers in the TS, $-N^{{\delta}+}{\cdots}S^{{\delta}-}-$, are in close vicinity increasing the interaction between nucleophile and leaving group. The inverse secondary kinetic isotope effects ($k_H/k_D$ < 1.0) are observed with deuterated benzylamines $(XC_6H_4CH_2ND_2)$.

Electrochemical Study of Poly(aniline N-alkylsulfonate)s

  • Kim, Eunkyoung;Rhee, Suh Bong
    • 분석과학
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    • 제8권4호
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    • pp.631-636
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    • 1995
  • Electrochemical properties of self-dopable poly(aniline N-butylsulfonate)s in various acidic medium were investigated by spectroelectrochemical techniques. Cyclic voltammetric study showed more than two reversible process of one electron transfer, the potential and peak intensity of which were dependent on the acid concentration and dopant ion. Spectroscopic study at different oxidation level indicated that the electrochromic switching of the poly(aniline N-alkylsulfonate)s film involves structural changes from benzenoid ring to quinoid ring. Spectrocyclic voltammetry together with impedance spectra of the PANBUS film in 0.1 M $LiClO_4$ solution of acetonitrile containing 0.46 M of perchloric acid showed two types of highly conductive states at the intermediate oxidation levels, which can be related to the metallic polaron states doped by two different process.

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Application of the Extended Grunwald-Winstein Equation to the Solvolyses of Phenyl Methanesulfonyl Chloride in Aqueous Binary Mixtures

  • Koh, Han-Joong;Kang, Suk-Jin
    • Bulletin of the Korean Chemical Society
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    • 제32권6호
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    • pp.1897-1901
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    • 2011
  • This report shows the rates of solvolyses for phenyl methanesulfonyl chloride ($C_6H_5CH_2SO_2Cl$, I) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, 2,2,2-trifluroethanol (TFE) and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) are reported. Three representative solvents, studies were made at several temperatures and activation parameters were determined. The thirty kinds of solvents gave a reasonably precise extended Grunwald-Winstein plot, coefficient (R) of 0.954. The sensitivity values (l = 0.61 and m = 0.34, l/m = 1.8) of phenyl methanesulfonyl chloride (I) were smaller than those obtained for benzenesulfonyl chloride ($C_6H_5SO_2Cl$, II; l = 1.01 and m = 0.61) and 2-propanesulfonyl chloride ($(CH_3)_2CHSO_2Cl$, III; l = 1.28 and m = 0.64). As with the two previously studied solvolyses, an $S_N2$ pathway with somewhat ionization reaction is proposed for the solvolyses of I. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were determined and they are also in line with values expected for a bimolecular reaction mechanism. The kinetic solvent isotope effect of 2.34 in $CH_3OH/CH_3OD$ is in accord with a bimolecular mechanism, probably assisted by general-base catalysis.

Correlation of the Rates of Solvolysis of 4-Morpholinecarbonyl Chloride Using the Extended Grunwald-Winstein Equation

  • Kim, Ran;Ali, Dildar;Lee, Jong-Pal;Yang, Ki-Yull;Koo, In-Sun
    • Bulletin of the Korean Chemical Society
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    • 제31권7호
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    • pp.1963-1967
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    • 2010
  • The rates of solvolysis of 4-morpholinecarbonyl chloride (MPC) have measured at $35.0^{\circ}C$ in water, $D_2O$, $CH_3OD$, and in aqueous binary mixtures of acetone, ethanol, methanol, and 2,2,2-trifluoroethanol. An extended (two-term) Grunwald-Winstein equation correlation gave sensitivities towards changes in solvent nucleophilicity and solvent ionizing power as expected for a dissociative $S_N2$ and/or $S_N1$(ionization) pathway. For nine solvents specific rates were determined at two additional temperatures and higher enthalpies and smaller negative entropies of activation were observed, consistent with the typical dissociative $S_N2$ or $S_N1$(ionization) pathway. The solvent deuterium isotope effect values for the hydrolysis of MPC of $k_{H_2O}/k_{D_2O}$ = 1.27 and for the methanolysis of MPC of $k_{MeOH}/k_{MeOD}$ = 1.22 are typical magnitudes of the $S_N1$ or ionization mechanism.

3-페닐-1-이소퀴놀린아민이 신경세포에서 베타 아밀로이드 전구단백질의 대사에 미치는 영향 (Effects of 3-Phenyl-1-isoquinolinamine on the Metabolism of ${\beta}$-Amyloid Precursor Protein in Neuroblastoma Cells)

  • 임재윤;조원제
    • 약학회지
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    • 제54권6호
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    • pp.529-534
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    • 2010
  • Alzheimer's disease (AD) is characterized pathologically by the presence of intracellular neurofibrillary tangles and deposition of ${\beta}$-amyloid ($A{\beta}$) peptides, which are generated by processing of amyloid precursor protein (APP). It is urgent to develop effective therapies for the treatment of AD, since our society rapidly accelerate aging. $A{\beta}$ peptides have been believed to be neurotoxic and now are also considered to have effects on the mechanism of memory formation. Recently, we investigated that a quinoline compound from natural product reduced the secretion of $A{\beta}$ from the neuroblastoma N2a cells (NL/N cell line) overexpressing APPswe. In this study, 3-phenyl-1-isoquinolinamine, a synthetic isoquinoline compound was analyzed to determine its effects on the metabolism of APP. It inhibited the secretion of $A{\beta}$ peptides from the N2a NL/N cell line. Beta-site APP cleaving enzyme (BACE) fluorescence resonance energy transfer (FRET) assay revealed that it inhibited BACE activity in a dose dependent manner. Immunoblotting study showed that it inhibited APP stabilization and expression and it slightly increased the stablization and the expression of ${\gamma}$-secreatase component from the N2a NL/N cell line. We suggest that 3-phenyl-1-isoquinolinamine inhibits APP metabolism and $A{\beta}$ generation by the means of BACE inhibitory mechanism. This is the first report that 3-phenyl-1-isoquinolinamine inhibits the secretion of $A{\beta}$ peptides from neuroblastoma cells.