• Title/Summary/Keyword: stepwise

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Ab-initio 계산을 통한 비대칭 Diels-Alder 반응의 단계적 경로와 단일 반응 경로의 비교 연구

  • Son, Mun-Gi
    • Proceeding of EDISON Challenge
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    • 2013.04a
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    • pp.101-109
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    • 2013
  • Diels-Alder 반응은 유기합성에서 중요하게 다뤄지는 고리형성 반응으로 위치 선택성과 더불어 단일 단계 반응이기에 특이한 입체 선택성을 갖는 것으로 알려졌다. 그러나 실제로는 단계적 반응 경로도 존재할 수 있음을 발견하였는데, 이 경우에 갖는 위치 선택성과 입체 선택성은 달라질 가능성이 높다. Density Functional Theorem(DFT)로 계산한 결과, 비대칭 Diels-Alder 에 대해 단계적 반응의 경우에도 마찬가지로 유사 ortho 형태에 endo 지향성을 나타내었지만 대칭 Diels-Alder 반응에 비해 단계적 반응이 일어나기 힘들다는 결론을 얻을 수 있었다.

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Nucleophilic Substitution Reactions of Thiophenyl Phenylacetate with Benzylamines in Acetonitrile

  • 오혁근;김선경;이익춘
    • Bulletin of the Korean Chemical Society
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    • v.20 no.9
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    • pp.1017-1020
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    • 1999
  • The aminolysis reactions of thiophenyl phenylacetates with benzylamines are investigated in acetonitrile at 55.0℃. Relatively large selectivity parameters, βx≒ 1.5, βz = -1.5~-1.8 and βxz = 0.92 together with the valid reactivity-selectivity principle are consistent with stepwise acyl transfer mechanism with rate limiting expulsion of the leaving group, thiophenolate anion, from the tetrahedral intermediate, T ± . The first order kinetics with respect to the benzylamine concentration and the realtively large secondary kinetic isotope effect (kH / kD = 1.2-1.7) involving deuterated benzylamine nucleophiles suggest a four center type transition state in which concurrent leaving group departure and proton transfer are involved.

Aminolysis of Aryl Thiol-2-furoates and Thiol-2-thiophenates in Acetonitrile

  • 오혁근;이준용;이익춘
    • Bulletin of the Korean Chemical Society
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    • v.19 no.11
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    • pp.1198-1202
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    • 1998
  • Aminolysis of aryl thiol-2-furoates and thiol-2-thiophenates with benzylainines are investigated in acetonitrile at 50.0 ℃. Relatively large selectivity parameters, ρx(βx), ρz(βx) and ρxz (> 0) together with the valid reactivity-selectivity principle are consistent with a stepwise acyl transfer mechanism with rate-limiting expulsion of the leaving group, thiophenolate anion, from the tetrahedral intermediate, T±. The first-order kinetics with respect to the benzylamine concentration and the relatively large secondary kinetic isotope effect involving deuterated benzylamine nucleophiles suggest a four-center type transition state in which concurrent leaving group departure and proton transfer are involved.

Polymerization of Anisole Derivatives Containing Allyl or Chloromethyl Group Through Aromatic Electrophilic Substitution Reaction

  • 장지영;박필정;한만정
    • Bulletin of the Korean Chemical Society
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    • v.18 no.12
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    • pp.1288-1291
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    • 1997
  • 4-Allylanisole was polymerized with AlCl3 as a catalyst. The polymerization was carried out in nitroethane at various temperatures with changing the ratio of the initiator to the monomer concentration. The weight averge molecular weights measured by gel permeation chromatography in chloroform with polystyrene standards were between 1,500 and 4,700. 1H NMR spectroscopy showed that the polymerization proceeded through a stepwise aromatic electrophilic substitution reaction along with a minor chain-reaction, resulting in a branched polymer. 4-Chloromethylanisole was also polymerized with AlCl3 in nitroethane through an aromatic electrophilic substitution reaction to give a high molecular weight polymer (Mw=88,000).

Continuous methanol synthesis directly from methane and steam over Cu(II)-exchanged mordenite

  • Lee, Sae Ha;Kang, Jong Kyu;Park, Eun Duck
    • Korean Journal of Chemical Engineering
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    • v.35 no.11
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    • pp.2145-2149
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    • 2018
  • The formation of methanol directly from methane and steam was observed over Cu ion-exchanged mordenite. Furthermore, the continuous production of methanol was achieved by co-feeding methane and steam over Cumordenite. The methanol production rate was comparable to that reported in the stepwise process in which activation, methane reaction, and extraction of methanol were carried out separately.

Michael-type Reactions of 1-(X-substituted phenyl)-2-propyn-1-ones with Alicyclic Secondary Amines in MeCN and H2O: Effect of Medium on Reactivity and Transition-State Structure

  • Kim, Song-I;Hwang, So-Jeong;Park, Yoon-Min;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.31 no.5
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    • pp.1199-1203
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    • 2010
  • Second-order rate constants ($k_N$) have been measured spectrophotometrically for Michael-type reactions of 1-(X-substituted phenyl)-2-propyn-1-ones (2a-f) with a series of alicyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The $k_N$ value increases as the incoming amine becomes more basic and the substituent X changes form an electron-donating group (EDG) to an electron-withdrawing group (EWG). The Br${\o}$nsted-type plots are linear with ${\beta}_{nuc}$ = 0.48 - 0.51. The Hammett plots for the reactions of 2a-f exhibit poor correlations but the corresponding Yukawa-Tsuno plots result in much better linear correlations with ${\rho}$ = 1.57 and r = 0.46 for the reactions with piperidine while ${\rho}$ = 1.72 and r = 0.39 for those with morpholine. The amines employed in this study are less reactive in MeCN than in water for reactions with substrates possessing an EDG, although they are ca. 8 pKa units more basic in the aprotic solvent. This indicates that the transition state (TS) is significantly more destabilized than the ground state (GS) in the aprotic solvent. It has been concluded that the reactions proceed through a stepwise mechanism with a partially charged TS, since such TS would be destabilized in the aprotic solvent due to the electronic repulsion between the negative-dipole end of MeCN and the negative charge of the TS. The fact that primary deuterium kinetic effect is absent supports a stepwise mechanism in which proton transfer occurs after the rate-determining step.

The Effect of Health Promotion Behavior on Fatigue and Depression among Shift Nurses (교대근무 간호사의 건강증진행위가 피로와 우울에 미치는 영향)

  • Lee, Eun-Ju;Shin, Seung-Wha
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.15 no.4
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    • pp.2256-2264
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    • 2014
  • This study was a descriptive study to identify the effect of health promoting behavior on fatigue and depression and to investigate these levels among nurses. Data were collected from September 19th 2012 to September 25th 2012 by questionnaires from 243 hospital nurses of 3 hospitals in Kyungsang-Bukdo. The data was analyzed using descriptive statistics, t-test, Pearson's correlation coefficients, ANCOVA, and Stepwise multiple regression. The result showed that in health promoting behavior, shift nurses had higher scores than it of non-shift nurses. The health promotion behavior predictors of fatigue were spiritual growth and stress management and the predictors of depression were physical activity and interpersonal relationship. This results suggest that development of professional health promoting program which is strengthened these parts of spiritual growth, stress management, physical activity and interpersonal relationship, is needed.

Predicting Risk Factors for Pressure Sores in Patients Undergoing Operations ; A Prospective Study (수술환자의 욕창예측변수에 관한 연구)

  • Pak Soon-Mi;Jun Seong-Sook
    • Journal of Korean Academy of Fundamentals of Nursing
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    • v.6 no.2
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    • pp.267-276
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    • 1999
  • The purpose of this study was to identify risk factors predictive of alterations in skin integrity during the intraoperative period. The predictive risk factors were studied for intraoperative pressure sores from December 1998 through January 1999. A sample of 220 patients was selected from the operating room schedule of a University Hospital in Pusan. There were two criteria in including patients : the operation lasted longer than 2 hours and the absence of skin break-down according to NPUAP criteria. The data were analized by SPSS/PC, Stepwise multiple logistic regression was used to identify the variables which were predictive of alterations in skin integrity. Of the 220 patients studied, 41 patients (18.6%) developed stage 1 pressure sores in the immediate postoperative period. In relation to skin changes, three independent variables emerged from the stepwise multiple logistic regression as being significant (p<0.05). Factors predictive of pressure sore formation included low serum albumin(p=0.000), prone position while undergoing surgery(p=0.0004), time on the operating table(p=0.0165). Among the intrinsic factors, serum albumin was the most significant causal factor in pressure sores development in the intra-operative period. Pressure and shearing force were the most significant extrinsic factors in pressure sores development. From the results of this study we concluded that the primary nursing goal is the maintenance of the proper patient' position during the intraoperative period. Also imperative for sore prevention is the reduction of surgery time and improving preoperative nutritional status.

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Factors Effect on Quality of Life of Spinal Cord Injury Patients (척수 손상 환자의 삶의 질 영향요인 분석)

  • 신성례;김애리
    • Journal of Korean Academy of Nursing
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    • v.31 no.1
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    • pp.126-138
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    • 2001
  • The purpose of this study is to act nursing intervention strategies to promote quality of life (QOL) in Spinal Cord Injury patients. Therefore, the study is designed to evaluate religion, marital status, educational background economic status, level of injury, voiding pattern, transportation by driving, rehabilitation education, self-concept, sexual status, perceived barrier, powerlessness, depression, hope, social support, self-efficacy, anxiety, ADL, perceived hopelessness, personality and pain for QOL at the same time. It was gathered empirical data was collected using a self report questionnaire from 61 patients during a six month period after SCI at 5 general hospitals, at 2 rehabilitation centers and at 2 rehabilitation schools province from Jun. 18, 1999 through Sep. 28, 1999. The reliability of the 19 instruments was tested with Cronbach's alpha which ranged from .6319 to .9769. For the data analysis a SAS program was used for Pearson correlation coefficients, and stepwise multiple regression. The results were as follows; 1. The mean of total item score in the QOL scale was 2.814, which showed a much lower score than the cancer points. 2. There was a significant correlation between self concept, transportation by driving, perceived barrier, powerlessness, depression, hope, social support, self-efficacy, anxiety, ADL and QOL.(${\gamma}$= .27~-.79, p< .05) 3. Stepwise multiple regression analysis showed that; a) Depression was the main predictor of QOL and account for 53.7% of the variance in QOL. b) Hope, ecomic status and body satisfaction accounted for 8%, 4%, 3.4% respectively and these variables combined accounted for 69.2% of the variance in QOL. In conclusion, to begin with, it is important to reduce depression and to help for SCI points to inspire hope, economic status and body satisfaction. That will be short cut for nursing strategies to enhance QOL.

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