• 제목/요약/키워드: $S_N1$ mechanism

검색결과 717건 처리시간 0.025초

Investigation of the effect of Erythrosine B on a β-amyloid (1-40) peptide using molecular modeling method

  • Lee, Juho;Kwon, Inchan;Cho, Art E.;Jang, Seung Soon
    • EDISON SW 활용 경진대회 논문집
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    • 제4회(2015년)
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    • pp.14-23
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    • 2015
  • Alzheimer's disease is one of the most common types of degenerative dementia. As a considerable cause of Alzheimer's disease, neurotoxic plaques composed of 39 to 42 residue-long amyloid beta($A{\beta}$) fibrils have been found in the patient's brain in large quantity. A previous study found that erythrosine B (ER), a red color food dye approved by FDA, inhibits the formation of amyloid beta fibril structures. Here, in an attempt to elucidate the inhibition mechanism, we performed molecular dynamics simulations to demonstrate the conformational change of $A{\beta}40$ induced by 2 ERs in atomistic detail. During the simulation, the ERs bound to the surfaces of both N-terminus and C-terminus regions of $A{\beta}40$ rapidly. The observed stacking of the ERs and the aromatic side chains near the N-terminus region suggests a possible inhibition mechanism in which disturbing the inter-chain stacking of PHEs destabilizes beta-sheet enriched in amyloid beta fibrils. The bound ERs block water molecules and thereby help stabilizing alpha helical structure at the main chain of C-terminus and interrupt the formation of the salt-bridge ASP23-LYS28 at the same time. Our findings can help better understanding of the current and upcoming treatment studies for Alzheimer's disease by suggesting inhibition mechanism of ER on the conformational transition of $A{\beta}40$ at the molecular level.

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살충제 buprofezin의 가수분해 반응 메카니즘 (Kinetics and mechanism of hydrolysis of insecticidal buprofezin)

  • 성낙도;유성재;최경섭;권기성
    • 농약과학회지
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    • 제2권1호
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    • pp.46-52
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    • 1998
  • [ $45^{\circ}C$ ]의 15%(v/v) dioxane 수용액중에서 살충성 buprofezin(IUPAC : tert-butylimino-3-iso-propyl-5-phenylperhydro-1,3,5-thiadiazin-4-one)의 가수분해 반응속도상수와 pka상수(5.60)를 측정하고 pH-효과, 용매효과(m=0.34, n=2.45 및 $1{\gg}m$), 열역학적 활성화 파라미터(pH 4.0, ${\Delta}H^{\neq}$= 11.12 $kcal{\cdot}mol^{-1}$, ${\Delta}S^{\neq}$=-5.0e.u. 및 $E_{act.}$=11.76Kcal), 반응 속도식등의 반응 속도론적 및 생성물분석(1-isopropyl-3-phenyl urea) 등의 비속도론적 실험결과를 얻었다. 이들 자료의 검토로부터 pH 8.0이하의 산성용액에서는 특정($k_{H3O+}$)및 일반 산-촉매반응에 의한 $A-S_{E}2$형 및 A-2(또는 $A_{AC}2$)형 반응, 그리고 pH 9.0이상의 알카리성 용액에서는 일반염기 촉매반응($k_{H2O}$)에 의한 친핵성 첨가-제거 ($Ad_{N}-E$) 반응이 사면체($sp^{3}$) 중간체를 경유하는 궤도-조절 반응으로 진행되는 일련의 가수분해 반응메카니즘을 제안하였다. 또한, Buprofezin은 산성(pH8.0이하)용액보다 염기성(pH8.0이상) 용액중($k=10^{-8}sec.^{-1}$)에서 더욱 안정하였으며 $45^{\circ}C$의 중성(pH 7.0) 수용액 중에서 반감기($t=\frac{1}{2}$)는 약 3개월이었다.

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Diastereoselective Synthesis of Unsaturated 1,4-Amino Alcohols as a Biologically Important Moiety

  • Jung Young Hoon;Kim Ji Duck
    • Archives of Pharmacal Research
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    • 제28권4호
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    • pp.382-390
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    • 2005
  • chial allylic ethers with a hydroxyl group attached to the $\pi-system$ and chlorosulfonyl isocyanate. The enantioselectivity of the CSI reaction with the chiral allylic and benzylic ethers was examined in various solvents and temperatures. Based on these results, it was proposed that the CSI reaction is a competitive reaction of a $S_{N}i$ (retention) and a $S_{N}1$ mechanism (racemization) according to the stability of the carbocation intermediate. This means that there is a greater proportion of retention with the less stable the carbocation intermediate and vise versa.

제초성 Flazasulfuron의 Smile 자리옮김 반응 (Smile Rearrangement of Herbicidal Flazasulfuron)

  • 이광재;김용집;김대황;성낙도
    • Applied Biological Chemistry
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    • 제39권1호
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    • pp.70-76
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    • 1996
  • 일련의 pyridylsulfonyl urea들을 합성하고 25%(v/v) 디옥산 수용액의 넓은 pH범위에서 가수분해 반응속도 상수를 측정하였다. pH-효과, 용매 효과($m{\ll}1,\;n{\ll}3$${\mid}m{\mid}{\ll}{\mid}{\ell}{\mid}$), 일반 염기-효과, 산-해리상수(pKa, 3: 4.9 및 5: lit.4.6), 열역학적 활성화 파라미터(${\Delta}H^{\neq}=0.025\;Kcal.mol.^{-1}$${\Delta}S^{\neq}=0.54{\sim}\;-2.19\;e.u.$) 및 생성물 분석 결과로부터 반응속도식을 유도하고 가수분해 반응 메카니즘을 제안하였다. 즉, 비(H)치환체, 1-(4,6-dimethoxypyrimidine-2-yl)-3-(2-pyridylsulfonyl) urea, 3은 산성용액에서 A-2형(또는 $A_{AC}2$)반응 그리고 염기성 용액 에서는 $(E_1)_{anion}$ 메카니즘으로 가수분해 반응이 일어난다. 반면에 trifluoromethyl-치환체, 1-(4,6-dimethoxypyrimidine-2-yl)-3-(3-trifluorornethyl-2-pyridylsulfonyl) urea, 5(Flazasulfuron)는 산성 용액중에서 $A-S_N2Ar$형의 반응으로 생성된 conjugate acid($5H^+$), 그리고 pH 9.0 이상에서는 $(E_1)_{anion}$$(E_1CB)_R$ 반응으로 생성된 conjugate base(CB)를 거쳐 산성 및 염기성 용액중에서 모두 5원자 고리 중간체를 경유하는 Smile 자리옮김 반응으로 산성에서는 3-trifluoromethyl-2-pyridylpyrimidinyl urea(PPU) 그리고 염기성에서는 3-trifluoromethyl-2-pyridyl-4,6-dimethoxy-pyrimidinyl amine(PPA)을 생성하는 가수분해 반응이 일어남을 알았으며 5는 3보다 약 3.5배 빠른 반응속도를 나타내었다.

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레이디얼 피스톤 펌프의 피스톤 접촉 메커니즘 개발 (Development of piston contact mechanism for radial piston pump)

  • 함영복;차재곤;김대명;공태우;윤소남;안국영;권병수
    • 유공압시스템학회논문집
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    • 제7권1호
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    • pp.1-5
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    • 2010
  • This paper presents the experimental results of the radial piston type oil pump with new mechanism for a metal diaphragm hydrogen compressor. Generally, metal diaphragm type hydrogen compressor systems are operated by oil hydraulic power. In this system an oil compensating pump has been demanded to compensate for a leakage oil head chamber. The metal diaphragm type hydrogen compressor consists of an oil compensating pump, commonly used hydraulic piston pump and driven by main crank shaft. The radial piston type oil compensating pump with new rolling contacted piston mechanism is developed and experimented. The developed piston element of the radial piston pump consists of piston, steel ball, return spring, two check valves, eccentric cam and ball racer. In this study, designed 4 type pistons as and orifice hole. Operating characteristics and pressure ripple characteristics are tested under no load to 60bar loaded with every 20bar increasing step and pressure ripple and flow rate are experimentally investigated.

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이중층 시료에서 확산에 의한 BiPbSrCaCuO 초전도체 개발 (Development of BiPbSrCaCuO Superconductor by Diffusion of Dual-Layer Sample)

  • 최성환;박성진;유현수;강형곤;한병성
    • 대한전기학회논문지
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    • 제43권5호
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    • pp.795-801
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    • 1994
  • The BiPbSrCaCuO superconductor was fabricated by diffusion of The dual layer composed of SrS12TCaS11TCuS12TOS1xT in upper layer and BiS12TPbSI0.3TCuS12TOS1yT in lower layer, and varified growh-mechanism of BiPbSrCaCuO superconducting phase. And, we produced optimum conditions of spread volume and each stage of sintering time were upper layer:Lower layer=1:0.2, 1:0.4, 1:0.6 and 24hr., 120hr., 210hr. From the result, the optimum conditions are spread volume(Upper layer:Lower layer=1:0.6), sintering time(210hrs.) at 820$^{\circ}C$.The BiPbSrCaCuO superconductor, fabricated optimum condition, showed zero resistance at critical temperature of 70k.

o-메틸염화벤질의 가용매분해반응에 대한 압력의 영향 (Pressure Effect on the Solvolysis of o-Methylbenzyl Chloride in Ethanol-Water Mixtures)

  • 권오천;경진범;신용균
    • 대한화학회지
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    • 제30권1호
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    • pp.40-46
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    • 1986
  • 온도 30$^{\circ}$와 40$^{\circ}$C에서 $o^-$메틸염화벤질의 가용매분해반응 속도를 에탄올 몰분율에 따라 압력을 1~ 1600 bar까지 변화시키면서 측정하였다. 이 반응의 속도 상수로부터 활성화부피 ${\Delta}V^{\neq}$, 활성화압축율 계수 ${\Delta}{\beta}^{\neq}$, 활성화 파라미터 ${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$, ${\Delta}G^{\neq}$를 구한 결과 electrostriction현상이 0.30에탄올 몰분율에서 extremum behavior가 나타남을 알았다. 그리고 Laidler - Eyring식을 적용하여 압력에 따른 가용매 분해반응 속도와 혼합용매의 유전상수와의 상관관계를 알아 보았고, 또한 반응메카니즘 변화를 검토하기 위하여 전이상태에서 반응에 관여한 물분자수를 계산하여 메카니즘의 성격을 고찰하였다. 이러한 사실로 부터 전이상태에서 반응은 bond-breaking이 지배적인 반응으로 진행되며, 압력증가와 물 함량감소에 따라 $S_N$1형의 반응 메카니즘 성격이 약화됨을 알았다.

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Pseudomonas sp. strain DJ77에 존재하는 Glutathione S-Transferase 아미노 말단잔기의 Site-directed Mutagenesis

  • 우희종;박용춘;김성재;정용제;정안식;김영창
    • 한국미생물·생명공학회지
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    • 제25권4호
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    • pp.374-378
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    • 1997
  • Glutathione S-transferase (GST) was purified from Pseudomonas sp. DJ77, and its N-terminal sequence was determined to be MKLFISPGACSL. A specific tyrosyl residue in the vicinity of the N terminus is conserved in all the known cytosolic GSTs and has been shown to function as a catalytic residue in $\alpha$, $\mu$, $\pi$ class GSTs from mammals. However, Pseudomonas sp. DJ77 GST has the Phe-4 and Ile-5 instead of Tyr in N-terminus. Its replacement with tyrosine did not significantly affect the enzyme activity. Results from in vitro biochemical analyses were confirmed by the in vivo activity-based CDNB growth inhibition analyses. Our results clearly indicate that GST of Pseudomonas sp. DJ77 has a novel reaction mechanism different from that of mammalian GSTs.

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5절 평면형 메커니즘의 동적 포복에 관한 연구 (Study on Dynamic Crawling of The Five-bar Planar Mechanism)

  • 이정헌;임남식;김희국;이병주
    • 한국정밀공학회:학술대회논문집
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    • 한국정밀공학회 2005년도 춘계학술대회 논문집
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    • pp.1045-1049
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    • 2005
  • In this paper, the dynamic crawling of a five-bar planar mechanism is investigated. One complete cycle of the crawling selected in this study consists of four different steps, i) sliding at one contact point between the mechanism and the ground, ii) changing its configuration without sliding at two contact points, iii) sliding at the other contact point, and iv) again changing its configuration without sliding at two contact points. In this type of crawling, the crawling mechanism maintains the shape of the parallel structure throughout a complete crawling cycle. The modeling algorithm for serial manipulators proposed by M. Thomas and et al.[1] is employed by introducing imaginary joints and links which represent the contact interfaces between the one end of the mechanism and the ground, while the other end of the mechanism is regarded as an end-effector of the imaginary serial manipulator which treats the reaction force and torque at the contact point as external forces. Then, a complete cycle of dynamic crawling of the mechanism is investigated through various computer simulations. The simulation result show that the stable crawling characteristics of the mechanism could be secured when the proper configurations depending on specified frictional constraints are met.

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전달각을 고려한 조향기구의 최적합성 (Optimal Synthesis of Steering Mechanisms Considering Transmission Angles)

  • 박종근
    • 한국기계가공학회지
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    • 제11권1호
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    • pp.68-75
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    • 2012
  • In this study, the optimal synthesis of planar steering mechanisms for vehicles is studied. The author minimized the steering error between two front wheels subject to the constraints of transmission angles. Nonlinear programming methods such as BFGS method and golden section search method are used for this optimization. As numerical examples, Ackermann's steering mechanism, 6-link and 10-link planar mechanism are adopted to check the usefulness of this method. Consequently, among the three optimized mechanisms, 10-link planar one conducts far more accurate performance subject to tight constraints of transmission angles.