• 제목/요약/키워드: $S_N1$ mechanism

검색결과 717건 처리시간 0.028초

Kinetic Studies on the Structure-Reactivity of Aryl Dithiomethylacetates

  • Oh, Hyuck-Keun;Park, Jie-Eun;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • 제25권7호
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    • pp.1041-1045
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    • 2004
  • Kinetic studies of the pyridinolysis $(XC_5H_4N)$ of aryl dithiomethylacetates $(CH_3CH_2C(=S)SC_6H_4Z,\;1)$ are carried out in acetonitrile at $60.0^{\circ}C$. A biphasic Bronsted plot is obtained with a change in slope from a large $({\beta}X\;{\cong}\;0.8)$ to a small $({\beta}X\;{\cong}\;0.2)$ value at $pK_a^{\circ}$ = 5.2, which is attributed to a change in the rate limiting step from breakdown to formation of a zwitterionic tetrahedral intermediate, $T^{\pm}$, in reaction path as the basicity of the pyridine nucleophile increases. This mechanism is supported by the change of the cross-interaction constant ${\rho}xz$ from a large positive ( ${\rho}xz$ = +1.36) for the weakly basic pyridines to a small negative ( ${\rho}_xz$ = -0.22) value for the strongly basic pyridines. The magnitudes of ${\rho}z$ and activation parameters are also consistent with the proposed mechanism.

균등 부하분산과 응답 정확도 향상을 위한 처리 이전 기법 (Migration Mechanism of Communication Process for Load Balancing and Accuracy Improvement)

  • 이신은;윤군재;최훈
    • 정보과학회 컴퓨팅의 실제 논문지
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    • 제22권1호
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    • pp.26-31
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    • 2016
  • Migrim(Migration enhanced Grid Middleware)은 임베디드 단말과 다중 서버들 간의 통신 미들웨어이다. 기존의 통신 미들웨어는 단말이 서버의 자원 상태를 알지 못하기 때문에, 특정 서버에 부하가 집중될 경우에도 그 서버로 계속 요청을 보내는 문제가 있다. 또한 단말은 서버가 가진 정보를 알 수 없기 때문에, 트랜잭션 처리 결과에 대한 정확도를 보장하기 어렵다. 병목현상과 응답 정확도 문제 해결을 위해, 본 논문에서는 Migrim에 적용한 커넥션 이전과 트랜잭션 이전 기법을 제안한다. 커넥션을 다른 서버로 위임하는 과정인 커넥션 이전을 통해 전체 서버에 부하를 균등하게 분산시킬 수 있고, 트랜잭션 처리를 다른 서버로 위임하는 과정인 트랜잭션 이전을 통해 응답의 정확도를 높일 수 있다.

Trichoplusia ni 세포의 apoptosis 메커니즘 규명을 위한 기초연구 (Basic Studies on the Apoptosis Mechanism of Trichoplusia ni Cell Line)

  • 이종민;양재명;이윤형;정인식
    • Applied Biological Chemistry
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    • 제44권1호
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    • pp.1-6
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    • 2001
  • 본 연구에서는 Ttichoplusia ni 세포의 apoptosis 유도 및 억제 현상의 기초연구를 수행하였다. Apoptosis 유도제로 알려진 hygromycin B에 의한 세포 성장 저해는 $200\;{\mu}/ml$의 수준에서부터 나타났고, $400\;{\mu}/ml$ hygromycin B를 처리한 세포에서는 배양 후 2일부터 DNA가 분절되어지는 것을 확인할 수 있었다. 그러나 dexamethasone과 sodium butyrate를 첨가시 세포성장은 저해되었지만 DNA 분절현상이 보이지 않아 apoptosi의 유발여부를 확인할 수 없었다. 그리고 caspase 기능억제제의 apoptosis 지연효과를 보기 위해 $200\;{\mu}/ml$ hygromycin B로 apoptosis를 유발한 상태에서 Ac-DEVD-CHO를 첨가하여 세포성장을 비교해 본 결과 이 저해제에 의해 약 36%정도 apoptosis가 억제되었음을 확인하였다. N-acetylcysteine의 경우도 apoptosis지연 효과가 있었다. Bcl_계에 속하는 anti-apoptotic 유전자의 발현연구로서 apoptosis 저해 단백질인 bcl-2 유전자를 곤충세포에 형질전환시킨 후 이 단백질이 한시적으로 발현되는 것을 western blot분석법으로 확인하였으며 apoptosis가 지연된 곤충세포주의 개발이 가능하다는 결론을 보였다.

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Hydro Dynamic Model을 이용한 CMOS의 파괴특성의 Transient Simulation해석 (Transient Simulation of CMOS Breakdown characteristics based on Hydro Dynamic Model)

  • 최원철
    • 한국산업융합학회 논문집
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    • 제5권1호
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    • pp.39-43
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    • 2002
  • In present much CMOS devices used in VLSI circuit and Logic circuit. With increasing a number of device in VLSI, the confidence becomes more serious. This paper describe the mechanism of breakdown on CMOS, especially n-MOS, based on Hydro Dynamic model with device self-heating. Additionally, illustrate the CMOS latch-up characteristics on simplified device structure on this paper.

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비례감압밸브의 압력제어특성 (Pressure Control Characteristics of Proportional Pressure Reducing Valve)

  • 윤소남;함영복;조정대
    • 동력기계공학회지
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    • 제7권1호
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    • pp.68-73
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    • 2003
  • The purpose of this study is to develop a new proportional pressure reducing valve and to verify the validity of a new mechanism with pressure control pin. The dynamic characteristics of the object pressure reducing valve was studied by numerical analysis of the mathematical model. Also, static and dynamic characteristics of the new pressure control valve were tested with a testing system based on the test standard.

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대장균에서 4-nitroquinoline 1-oride의 변이원성에 대한 숙지황 물추출물의 항돌연변이 작용특성 (Antimutagenic Mechanism of Water Extract from Rehmannia glutinosa Liboshitz on 4-nitroquinoline 1-oxide Induced Mutagenesis n E. coli B.r)

  • 안병용;한종현;최동성
    • KSBB Journal
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    • 제16권5호
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    • pp.486-492
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    • 2001
  • 숙지황 물추출물로부터 분리된 fraction(RG-III) 의 항돌연변이원성의 기작을 E. coli GW, B/r 균주를 이용하여 조사하였다. SOS 유도를 반영하는 $\beta$-galactiosidase 활성이 E. coli GW 1060, 1103, 1107, 1105에서 증가되지 않았다. RG-III는 RecA는 단백질의 합성을 증폭시키거나 LexA 산물의 분해를 저해하지 않았으므로 SOS en 기능의 발현이 영향을 미치지 못했다. 따라서 DNA 수복의 경로가 다른 E. coli B.r 변이주를 사용하여 4NQO와 MNNG에 대한 세포내 항돌연변이원성과 생존효과를 조사하였다. ZA159(uvrB, 최)를 제외한 WP2, WP2s, WP67, CM561, CM611에서 RG-III는 4NQO에 대한 생존력을 미약하게나마 증가시켰으나, 이러한 생존력 재활성을 수복모드에 의해 설명할 수 없었다. WP2, WP2s, WP67, CM561, CM611에서 RG-III는 MNNG로 유도된 돌연변이원성과 치사력을 증가시킴에도 불구하고 ZA159(uvr B, chl)에서는 감소시켰다. 4NQO의 변이원성을 두드러지게 억제하였으나 ZA159(uvr B, chl)에서 상승효과가 상대적으로 감소되었다. 이러한 결과들은 RG-III가 4NQO의 변이원성을 방어하는 차단제임을 시시하여, chl 산물의 기능과 유사한 작용을 하는 것으로 사료된다.

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Effect of the Volatile Oil of Nigella sativa Seeds and Its Components on Body Temperature of Mice: Elucidation of the Mechanisms of Action

  • Ashour, M.M.;Tahir, K.E.H.El.;Morsi, M.G.;Aba-Alkhail, N.A.
    • Natural Product Sciences
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    • 제12권1호
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    • pp.14-18
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    • 2006
  • The effect(s) of the volatile oil (VO) of Nigella sativa and its two components, ${\alpha}-pinene$ and ${\rho}-cymene$ on body temperature of male and female conscious mice were studied. Further investigations to delineate the mechanism(s) of action of the observed effect(s) by using various blockers involved in the central regulation of body temperature were made. VO and ${\alpha}-pinene$ caused significant reductions in rectal body temperature at is and 30 minute after treatment. ${\rho}-cymene$ had negligible effect on body temperature of mice. Cyproheptadine inhibited VO and ${\alpha}-pinene-induced$ hypothermia significantly. Nalbuphine inhibited ${\alpha}-pinene-induced$ hypothermia significantly but did not affect VO-induced hypothermia. Droperidol potentiated VO and ${\alpha}-pinene-induced$ hypothermia to a non-significant level; whereas atropine potentiated VO-induced hypothermia non-significantly. The study confirms further the role of serotoninergic receptors in the mechanism(s) of the observed pharmacological effects of the VO of Nigella sativa. It also indicated a possible role of opioid receptors in ${\alpha}-pinene-induced$ hypothermia.

염화벤질류의 가용매분해반응에 대한 압력의 영향. 에탄올-물 혼합용매내에서 p-메톡시 염화벤질의 분해반응 (The Effect of Pressure on the Solvolysis of Benzylchlorides. p-Methoxybenzyl Chloride in Ethanol-Water Mixtures)

  • 권오천;경진범;최기준
    • 대한화학회지
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    • 제30권3호
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    • pp.301-306
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    • 1986
  • 에탄올-물 혼합용매내에서 p-메톡시 염화벤질의 가용매 분해 반응에 대한 속도상수를 온도 2$^{\circ}$와 10$^{\circ}C$, 압력을 1~1600bar로 변화시켜 가면서 측정하였다. 이 반응의 속도 상수(k)는 온도와 압력이 증가함에 따라 증가하고 에탄올 몰 분율이 증가함에 따라 감소함을 알았다. 또한 이 반응 속도 상수로 부터 (${{\Delta}V_o}^{\neq},\;{\Delta}{\beta}^{\neq},\;{\Delta}H^{\neq}$${\Delta}S^{\neq}$)의 값을 얻었다. 이 때 ${{\Delta}V_o}^{\neq}$${\Delta}{\beta}^{\neq}$는 에탄올 몰분율이 약 0.30인 부근에서 extremum behavior가 나타남을 알았고, 이러한 현상을 용매구조 변화로 논의하였다. 이러한 사실로부터 본 반응은 $S_N1$ 메타니즘이 지배적이며 압력이 증가함에 따라서는 $S_N1$ 성격이 약해짐을 알았다.

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제주도 연안해역을 중심으로 한 DMS 농도의 관측 (Dimethylsulfide (DMS) in the Coastal Areas of the Cheju Island, Korea)

  • 김기현;이강웅;허철구;강창희
    • 한국대기환경학회지
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    • 제13권2호
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    • pp.161-170
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    • 1997
  • The concentrations of dimethylsulfide (DMS) were determined using samples collected from a station located at Kosan, Cheju Island during two field campaigns held in December 1996 and January 1997. The atmospheric DMS concentrations measured at 6-hr intervals during the entire campaign periods, after excluding a few extreme values, spanned in the range of 14 to 410 pptv with mean and 1 SD value of 127 $\pm$ 94 pptv (N=42). Between two month periods during which the field campaigns were conducted, a notable reduction in DMS levels was observed which was comparable to the dramatic shift in air temperature. A considerable difference was also noted in DMS levels, when data were grouped by day/night basis. The cause of unexpected, high day-to-night DMS ratios is best explained in terms of high efficiency of daytime source processes relative to low efficiency of nighttime sink processes due to the characteristics of the study location. The surface water DMS of the study site, although scarcely measured, also behaved similarly to its atmospheric counterpart with its range from 0.3 to 19 nM (N=11). When correlation analysis was conducted between the atmospheric DMS concentration and other concurrently determined parameters, significant correlations were observed from most basic meteorological parameters such as windspeed, relative humidy, and air temperature. However, the existence of "not-so-strong" correlations between air temperature and DMS concentrations relative to other ones indicated that the effect of temperature on DMS behavior must be reflected in more complicated manners at the study site. The sea-to-air flux of DMS was approximated through an application of the mass-balance flux calculation method of Wylie and de Mora (1996) under the assumption that sink mechanism within the marine boundary layer is in steady-state condition with its counterpart, source mechanism. Based on this estimation method, we reached a conclusion that oceanic DMS emitted from the southwest sea of the Korean Peninsula can amount to approximately 9 $\sim$ 36 Gg S $yr^{-1}$.$yr^{-1}$.

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미세조직 변화에 따른 AISI 52100 강의 미끄럼마멸 특성 (Sliding Wear Behavior of AISI 52100 Steel with Pearlitic and Bainitic Microstructures)

  • 윤나래;김용석
    • 소성∙가공
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    • 제20권7호
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    • pp.479-484
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    • 2011
  • Dry sliding wear behavior of AISI 52100 steel that has a pearlite or bainite microstructure was characterized to explore the effect of microstructure on the wear of the steel. Isothermal heat treatments were employed to obtain the different microstructures. Pin-on-disk type wear tests of the steel disk were performed at loads of 25~125N in air against an alumina ball. Sliding speed and wear distance used were 0.1m/sec and 300m, respectively. Worn surfaces, wear debris and cross-sections of the worn surfaces were examined with SEM to investigate the wear mechanism of the steel. Hardness of the steel was also evaluated. Wear rate of the steel was correlated with the hardness and the microstructure. On the whole, wear resistance increased with an increase in hardness. However, the pearlite microstructure showed superior wear resistance as compared to the bainite microstructure with a similar hardness. The effect of the microstructure on the wear rate was attributed to the morphological differences of the carbide in the microstructure, which was found to have a significant effect on strain hardening during the wear.