• 제목/요약/키워드: $S_N2$ mechanism

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비수계분산매체에서 질화규소와 소결첨가제 AlN 및 Nd$_2$O$_3$의 분산 (Dispersion of Silicon Nitride Particles and Sintering Additives of AlN and Nd$_2$O$_3$ in Nonaqueous Suspending Media)

  • 김재원;백운규;윤경진
    • 한국세라믹학회지
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    • 제36권2호
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    • pp.210-219
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    • 1999
  • Alcohols, hydrocarbons, ketones 그리고 ethers와 같은 다양한 유기용매에서 질화규소 및 소결첨가제로 사용되는 AlN, Nd2O3 입자의 분산특성을 연구하였다. 분산안정화기구 및 유기공정첨가제와의 상호작용에 관한 연구를 수행하여 비수계 시스템에서 세라믹 입자의 분산성을 규명하였다. 현탁액의 물성특성은 산술된 Hamaker 상수 뿐 아니라 electrokinetic sonic amplitude 측정 및 유동학적 결과로부터 얻어진 흐름곡선을 이용하여 평가하였다. 유기용매 내에서 Si3N4, AlN 그리고 Nd2O3 분산안정화에 기여하는 정전기적 척력은 예상보다 컸으며, 이것은 유기용매의 물리화학적 특성에 의존함을 알 수 있었다.

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PHOTOCATALYTIC ISOQUINOLINE PRODUCTION AND N-ALKYLATION BY PLATINIZED TITANIUM(IV) OXIDE PARTICLES SUSPENDED IN ALCOHOLIC SOLUTION OF PHENETHYLAMINES

  • Bunsho Ohtani;Yoshiko Moriguchi;Nishimoto, Sei-Ichi;Tomoyuki Inui
    • Journal of Photoscience
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    • 제1권2호
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    • pp.107-111
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    • 1994
  • Photocatalytic ($\lambda$$_{ex}$ > 300 nm) reaction at room temperature by platinized titanium (IV) oxide particles produced 1-methyl-1, 2, 3, 4-tetrahydroisoquinolines (MIQ's) from phenethylamines in aqueous ethanol suspension under deaerated atmosphere. Among the phenethylamines, dopamine (2-(3, 4-dihydroxyphenyl) ethylamine) showed the highest reactivity to give MIQ almost selectively under the neutralized conditions. The other phenethylamines gave predominantly N-alkylated and N, N-dialkylated products in the methanol or ethanol solutions. The reaction mechanism includes a Schiff base intermediate to undergo either nucleophilic attack leading to MIQ or reduction to N-alkylated products.

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Arachidonic Acid Activates $K^+$-$Cl^-$-cotransport in HepG2 Human Hepatoblastoma Cells

  • Lee, Yong-Soo
    • The Korean Journal of Physiology and Pharmacology
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    • 제13권5호
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    • pp.401-408
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    • 2009
  • $K^+$-$Cl^-$-cotransport (KCC) has been reported to have various cellular functions, including proliferation and apoptosis of human cancer cells. However, the signal transduction pathways that control the activity of KCC are currently not well understood. In this study we investigated the possible role of phospholipase $A_2$ ($PLA_2$)-arachidonic acid (AA) signal in the regulatory mechanism of KCC activity. Exogenous application of AA significantly induced $K^+$ efflux in a dose-dependent manner, which was completely blocked by R-(+)-[2-n-butyl-6,7 -dichloro-2-cyclopentyl-2,3-dihydro-1-oxo-1Hinden-5-yl]oxy]acetic acid (DIOA), a specific KCC inhibitor. N-Ethylmaleimide (NEM), a KCC activatorinduced $K^+$ efflux was significantly suppressed by bromoenol lactone (BEL), an inhibitor of the calciumindependent $PLA_2$ ($iPLA_2$), whereas it was not significantly altered by arachidonyl trifluoromethylketone ($AACOCF_3$) and p-bromophenacyl bromide (BPB), inhibitors of the calcium-dependent cytosolic $PLA_2$ ($cPLA_2$) and the secretory $PLA_2$ ($sPLA_2$), respectively. NEM increased AA liberation in a doseand time-dependent manner, which was markedly prevented only by BEL. In addition, the NEM-induced ROS generation was significantly reduced by DPI and BEL, whereas $AACOCF_3$ and BPB did not have an influence. The NEM-induced KCC activation and ROS production was not significantly affected by treatment with indomethacin (Indo) and nordihydroguaiaretic acid (NDGA), selective inhibitors of cyclooxygenase (COX) and lipoxygenase (LOX), respectively. Treatment with 5,8,11,14-eicosatetraynoic acid (ETYA), a non-metabolizable analogue of AA, markedly produced ROS and activated the KCC. Collectively, these results suggest that $iPLA_2$-AA signal may be essentially involved in the mechanism of ROS-mediated KCC activation in HepG2 cells.

The Origin of Coercivity Enhancement of Sintered NdFeB Magnets Prepared by Dy Addition

  • Yu, N.J.;Pan, M.X.;Zhang, P.Y.;Ge, H.L.
    • Journal of Magnetics
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    • 제18권3호
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    • pp.235-239
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    • 2013
  • The effect of Dy addition on the microstructure and magnetic properties of the sintered NdFeB magnets was investigated. The results of the microstructure analysis showed that Dy-free and Dy-doped samples are composed of $Nd_2Fe_{14}B$ (P42/mnm) and a trace of Nd-rich phase. Dy addition reduces significantly the pole density factor of (004), (006) and (008) crystal faces as estimated by the Horta formula. Accordingly, the coercivity of the Dy-doped sample increases from 2038 $kA{\cdot}m^{-1}$ up to 2288 $kA{\cdot}m^{-1}$. The $H_{cj}(T)/M_s(T)$ versus $H^{min}_N/M_s(T)$ (Kronm$\ddot{u}$ller-plot) behavior shows that the nucleation is the dominating mechanism for the magnetization reversal in these two kinds of magnets, and two microstructural parameters of ${\alpha}_k$ and $N_{eff}$ are obtained. The Kronm$\ddot{u}$ller-Plot gives evidence for an increase of the ${\alpha}_k$ responsible for an increase of the coercivity as the result of the increase of the magnetic field as the magnetic domain reversed.

고압하에서 염화벤질의 가용매분해반응에 대한 속도론적 연구 (A Kinetic Study on the Solvolysis of Benzyl Chloride under High Pressure)

  • 권오천;경진범
    • 대한화학회지
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    • 제31권3호
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    • pp.207-214
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    • 1987
  • 염화벤질의 가용매분해반응에 대한 속도를 $1{\sim}1600bar$ 압력범위까지 변화시켜 가면서 온도 30 및 $40^{\circ}C$에서 측정하였다. In k대 압력의 실험결과는 압력에 따라 이차함수형으로 변화하였으며, 이로부터 활성화부피(${\Delta}V^{\neq}$)와 활성화 압축율(${\Delta}{\beta}^{\neq}$)의 값을 얻었다. In k를 용매파라미터($Q_w$) 및 ln $C_w$의 함수로 도시한 결과 이들 사이의 관계는 본 연구의 반응이 $S_N$1메카니즘으로 진행됨을 나타내었다. 이 전에 연구된 결과들과 비교한 결과 ${\mid}{{\Delta}V_0}^{\neq}{\mid}$와 n 값의 증가 순은 각각 p-Cl>p-H>p-$CH_3\;와\;p-$CH_3>p-H>p-Cl$이었다. 이로부터 $p-CH_3$ 치환체는 $S_N1(1)$ 성격이 강하며, 반면 p-Cl는 ${S_N}1(2)$ 성격이 나타남을 알았다.

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(感光性 高分子에 關한 硏究 VII) Cinnamoylated Polymers의 光增感 硬化反應機構 ((Photosensitive Polymers VII) Mechanism of Photosensitized Curing Reaction of Cinnamoylated Polymers)

  • 김광섭;심정섭
    • 대한화학회지
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    • 제10권4호
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    • pp.166-174
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    • 1966
  • cinnamoylated photosensitive polymer의 광증감 경화반응기구를 반응속도론적으로 연구했다. Cinnamic acid(C)와 증감제(S)의 first excited singlet and lowest triplet energy level diagram과 증감제의 농도증가에 따른 sensitivity의 포화 등의 사실로부터 이 반응의 주요과정은 C와 S의 광 energy흡수에 의한 $C^{*(1)}$$S^{*(1)}$로의 여기, $S^{*(1)}{\to}S^{*(3)}$ intersystem crossing, S의 excimer 형성, $S^{*(3)}{\to}C^{*(3)}$ energy transfer 그리고 $C^{*(3)}$와 C의 termination 등임을 가정하고 다음 반응속도를 구했다. $-\frac{d[C]}{dt} = \frac{K_1[C]}{K_2 + [C]}[\frac{I^c_{abs}}{K_3 + [S]} + \frac{K_4[C]}{(K_5 + [C])(K_6 + [S])}(I^s_{abs} + \frac{K_7I^c_{abs}[S]}{K_8 + [S]})]$ $I^c_{abs}$$I^s_{abs}$ ;C 및 S의 광흡수율 $K_n$;상수 적외선 흡수스펙트럼 분석의 결과, Cinnamoyl 에스테르화도와 sensitivity의 관계 및 증감제의 농도와 sensitivity의 관계에 대하여 발표된 실험 data는 윗식을 만족시키므로 가정한 반응기구에 대한 뒷받침을 얻었다.

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A New Chiral Stationary Phase Derived from Cyclohexylamide Derivative of (S)-Naproxen for the Liquid Chromatographic Resolution of Enantiomers

  • 현명호;이정배
    • Bulletin of the Korean Chemical Society
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    • 제16권10호
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    • pp.977-980
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    • 1995
  • A new chiral stationary phase (CSP 2) derived from cyclohexylamide of (S)-naproxen has been prepared. CSP 2 has shown greater enantioselectivities for the two enantiomers of N-(3,5-dinitrobenzoyl)-a-amino esters and amides than the CSP derived from 3,5-dimethylanilide of (S)-naproxen (CSP 1) as expected from the reciprocity conception of chiral recognition. However, CSP 2 has been found to be worse than CSP 1 in resolving N-(3,5-dinitrobenzoyl)-a-arylalkylamines, supporting the previously proposed chiral recognition mechanism which utilizes the 3,5-dimethylphenyl group of CSP 1 as an alternative π-basic interaction site. In addition, CSP 2 has been found to be reasonably good in resolving the two enantiomers of a variety of other π-acidic racemates.

Kinetics and Mechanism of the Anilinolysis of Bis(aryl) Chlorophosphates in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • 제32권6호
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    • pp.1939-1944
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    • 2011
  • The nucleophilic substitution reactions of bis(Y-aryl) chlorophosphates (1) with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at 35.0 $^{\circ}C$. The kinetic results of 1 are compared with those of Y-aryl phenyl chlorophosphates (2). The substrate 1 has one more identical substituent Y compared to substrate 2. The cross-interaction between Y and Y, due to additional substituent Y, is significant enough to result in the change of the sign of cross-interaction constant (CIC) from negative ${\rho}_{XY}$ = -1.31 (2) to positive ${\rho}_{XY}$ = +1.91 (1), indicating the change of reaction mechanism from a concerted $S_N2$ (2) to a stepwise mechanism with a rate-limiting leaving group departure from the intermediate (1). The deuterium kinetic isotope effects (DKIEs) involving deuterated anilines ($XC_6H_4ND_2$) show secondary inverse, $k_H/k_D$ = 0.61-0.87. The DKIEs invariably increase as substituent X changes from electron-donating to electron-withdrawing, while invariably decrease as substituent Y changes from electron-donating to electron-withdrawing. A stepwise mechanism with a rate-limiting bond breaking involving a predominant backside attack is proposed on the basis of positive sign of ${\rho}_{XY}$ and secondary inverse DKIEs.

Co-Deposition법을 이용한 Yb Silicide/Si Contact 및 특성 향상에 관한 연구

  • 강준구;나세권;최주윤;이석희;김형섭;이후정
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2013년도 제44회 동계 정기학술대회 초록집
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    • pp.438-439
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    • 2013
  • Microelectronic devices의 접촉저항의 향상을 위해 Metal silicides의 형성 mechanism과 전기적 특성에 대한 연구가 많이 이루어지고 있다. 지난 수십년에 걸쳐, Ti silicide, Co silicide, Ni silicide 등에 대한 개발이 이루어져 왔으나, 계속적인 저저항 접촉 소재에 대한 요구에 의해 최근에는 Rare earth silicide에 관한 연구가 시작되고 있다. Rare-earth silicide는 저온에서 silicides를 형성하고, n-type Si과 낮은 schottky barrier contact (~0.3 eV)를 이룬다. 또한, 비교적 낮은 resistivity와 hexagonal AlB2 crystal structure에 의해 Si과 좋은 lattice match를 가져 Si wafer에서 high quality silicide thin film을 성장시킬 수 있다. Rare earth silicides 중에서 ytterbium silicide는 가장 낮은 electric work function을 갖고 있어 낮은 schottky barrier 응용에서 쓰이고 있다. 이로 인해, n-channel schottky barrier MOSFETs의 source/drain으로써 주목받고 있다. 특히 ytterbium과 molybdenum co-deposition을 하여 증착할 경우 thin film 형성에 있어 안정적인 morphology를 나타낸다. 또한, ytterbium silicide와 마찬가지로 낮은 면저항과 electric work function을 갖는다. 그러나 ytterbium silicide에 molybdenum을 화합물로써 높은 농도로 포함할 경우 높은 schottky barrier를 형성하고 epitaxial growth를 방해하여 silicide film의 quality 저하를 야기할 수 있다. 본 연구에서는 ytterbium과 molybdenum의 co-deposition에 따른 silicide 형성과 전기적 특성 변화에 대한 자세한 분석을 TEM, 4-probe point 등의 다양한 분석 도구를 이용하여 진행하였다. Ytterbium과 molybdenum을 co-deposition하기 위하여 기판으로 $1{\sim}0{\Omega}{\cdot}cm$의 비저항을 갖는 low doped n-type Si (100) bulk wafer를 사용하였다. Native oxide layer를 제거하기 위해 1%의 hydrofluoric (HF) acid solution에 wafer를 세정하였다. 그리고 고진공에서 RF sputtering 법을 이용하여 Ytterbium과 molybdenum을 동시에 증착하였다. RE metal의 경우 oxygen과 높은 반응성을 가지므로 oxidation을 막기 위해 그 위에 capping layer로 100 nm 두께의 TiN을 증착하였다. 증착 후, 진공 분위기에서 rapid thermal anneal(RTA)을 이용하여 $300{\sim}700^{\circ}C$에서 각각 1분간 열처리하여 ytterbium silicides를 형성하였다. 전기적 특성 평가를 위한 sheet resistance 측정은 4-point probe를 사용하였고, Mo doped ytterbium silicide와 Si interface의 atomic scale의 미세 구조를 통한 Mo doped ytterbium silicide의 형성 mechanism 분석을 위하여 trasmission electron microscopy (JEM-2100F)를 이용하였다.

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