• 제목/요약/키워드: Rate Determining Step

검색결과 232건 처리시간 0.029초

대사과정(代謝過程)에 있어서 율속단계(律速段階) 결정(決定)에 관(關)한 연구(硏究) (I) - 발아종자자엽(發芽種子子葉)에 있어서 산소활성(酸素活性)에 미치는 광선(光線)의 영향(影響) - ((1) Studies on the Determination of the Rate Control Steps in the Various Metabolic Cycles (I) - The Affect of the Light to the Enzyme Activities in the Cotyledons of the Germinating Seeds -)

  • 신귀남
    • Applied Biological Chemistry
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    • 제3권
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    • pp.1-7
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    • 1962
  • In order to study the rate control step in the protein metabolic course of the chlorophyll formation, the transaminase activities which are obtained freely in the extracts of cotyledons of germinating peas at the light and the dark places, are measured in Beckman mopel D.U, spectrophoto meter at 490 mu. In this case, of two enzymatic reaction products; oxalacetic acid and pyruvic acid, the former is converted to pyruvic acid by aniline citrate and after each pyruvate phenyl hydrazones are extracted by toluenes: when this is treated with strong alcoholic alkali, a colored hydrazone is formed and it is measured by above apparatus. The estimated G.O.T. and G.P.T. in the germinated cotyledons at dark and light places considerably differ in their activities; G.O.T. and G.P.T. activities which are formed at the light are more increased than at the dark and also they differ in their rates through germination, though G.O.T. activity increment is smoothly but that of G.P.T. is more sharply, and they are considered to be directly affected to the chlorophyll formation and indirectly to the growth. G.O.T. and G.P.T. in each fractions of cell in the cotyledons should be formed by dissociation of zymogens in the microsomal fractions and it seems to promoted by light. In the formation of the chlorophyll, the protein metabolism occurred mainly in the microsomal fractions and the rate determining step is found at the point where the zymogene that is able to produce G.P.T. is activated, and this activation is promoted by light as noted above.

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회중석 정광의 염소화에 의한 텅스텐 성분의 추출 (Extraction of tungsten component from the scheelite concentrate by the chlorination)

  • 엄명헌;이철태
    • 공업화학
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    • 제4권1호
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    • pp.82-93
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    • 1993
  • 염소화 공정을 통해 batch-boat-system에서 회중석으로부터 텅스텐 성분을 추출하기 위해, 환원제인 탄소의 무게비, 반응온도, 반응시간, $Cl_2$ gas의 유량 그리고 시료입도와 같은 주요 반응 변수들에 대한 영향을 조사하였다. 이 염소화 공정들에 대한 적정조건들은 반응온도 $700^{\circ}C$ 이상, 광물시료에 대한 탄소의 무게비 0.08, 반응시간 20분, $Cl_2$ gas의 유량 $0.6{\ell}/min$, 광물시료의 입도 -200mesh였으며 위 조건하에서 광물중 99%의 tungsten성분이 추출되었다. 반응속도는 고온에서는 $Cl_2$ gas의 확산단계가, 저온에서는 화학반응단계가 속도결정단계로 보이며 각각의 단계에서 활성화 에너지는 고온 부분에서는 7.98kcal/mol이며 저온 부분에서는 31.2kcal/mol이었다.

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Kinetic Study on Nucleophilic Substitution Reactions of 4-Chloro-2-nitrophenyl X-Substituted-benzoates with Cyclic Secondary Amines: Effect of Substituent X on Reactivity and Reaction Mechanism

  • Jeon, Seong Hoon;Kim, Hyun Soo;Han, Young Joon;Kim, Min-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제34권10호
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    • pp.2983-2988
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    • 2013
  • Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of 4-chloro-2-nitrophenyl X-substituted-benzoates (1a-1h) with a series of cyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Hammett plot for the reactions of 1a-1h with piperidine consists of two intersecting straight lines, while the Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}_X $ = 1.25 and r = 0.58, indicating that the nonlinear Hammett plot is not due to a change in the rate-determining step (RDS) but is caused by ground-state stabilization through resonance interactions for substrates possessing an electron-withdrawing group in the benzoyl moiety. The Br${\o}$nsted-type plot for the reactions of 4-chloro-2-nitrophenyl benzoate (1d) with a series of cyclic secondary amines curves downward with ${\beta}_2$ = 0.85, ${\beta}_1$ = 0.24, and $pK_a{^o}$ = 10.5, implying that a change in RDS occurs from the $k_2$ step to the $k_1$ process as the $pK_a$ of the conjugate acid of the amine exceeds 10.5. Dissection of $k_N$ into the microscopic rate constants $k_1$ and $k_2/k_{-1}$ ratio associated with the reaction of 1d reveals that $k_2$ is dependent on the amine basicity, which is contrary to generally held views.

Aminolysis of 2,4-Dinitrophenyl and 3,4-Dinitrophenyl 2-Thiophenecarboxylates: Effect of ortho-Nitro Group on Reactivity and Mechanism

  • Seo, Jin-A;Chun, Sun-Mee;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제29권8호
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    • pp.1459-1463
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    • 2008
  • Second-order rate constants (kN) have been measured spectrophotometrically for reactions of 3,4-dinitrophenyl 2-thiophenecarboxylate (2) with a series of alicyclic secondary amines in 80 mol % $H_2O$/20 mol % dimethyl sulfoxide at 25.0 ${^{\circ}C}$. The Brønsted-type plot exhibits a downward curvature for the aminolysis of 2. The curved Brønsted-type plot is similar to that reported for the corresponding reactions of 2,4-dinitrophenyl 2- thiophenecarboxylate (1). The reactions of 1 and 2 have been suggested to proceed through the same mechanism, i.e., through a zwitterionic tetrahedral intermediate ($T^{\pm}$) with a change in the rate-determining step. Substrate 2 is less reactive than 1 toward weakly basic amines (e.g., $pK_a$ < 10.4) but becomes more reactive as the basicity of amines increases further. Dissection of kN into the microscopic rate constants has revealed that the reaction of 2 results in a smaller $k_2/k_{-1}$ ratio but larger $k_1$ than the corresponding reaction of 1. Steric hindrance exerted by the ortho-nitro group has been suggested to be responsible for the smaller $k_1$ value found for the reactions of 1.

Proposing provisions of Standard Repair Method of Painting Work Defect by Lawsuit Case Study

  • Seo, Deokseok
    • 교육녹색환경연구
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    • 제16권2호
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    • pp.1-9
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    • 2017
  • Defect dispute in apartment building has become a debating social issue. The system of defect lawsuit and the conciliation process are applicable to solve defect problems in South Korea. Among various defects, painting work defect is a critical issue because it requires large area works and entails a lot of cost. Accordingly, disputes on work procedure and cost calculation are argued oftenly between residents and housing providers. This study reviewed detailed main issues of painting work and propose relevant systems and standards. In this analysis, the main issues are categorized into pre-works, main work, and others. The most recent cases are compared and analyzed for each issue. After the analysis, following conclusions are obtained, (1) In defect lawsuit system, even though surface treatment work in pre-work step is part of main work, it has been separated and regarded as a separate work. (2) Although the main painting work are not significantly different from two systems, it is still necessary to achieve a consensus to close the gap in the methodology of painting area calculation and determining whole painting or partial painting. (3) In addition, unlike the profit rate of general construction works, that of painting work remained the maximum rate and additional charge rate for works carried out in higher place are different among cases. Therefore, it is determined that establishing consistent standards is urgent.

C. I. Disperse Blue 79의 알칼리 가수분해 반응속도 및 반응메카니즘 (Kinetics and Mechanism for Alkaline Hydrolysis of C. I. Disperse Blue 79)

  • 박건용;박창혁;박병기
    • 한국염색가공학회지
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    • 제13권5호
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    • pp.24-24
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    • 2001
  • Kinetics and mechanism for alkaline hydrolysis of C. I. Disperse Blue 79(B-79) which is 4-N, N-diacetoxyethyl-2-acylamino-5-ethoxy -2′-bromo-4′,6′-dinitroazobenzene were investigated. The color strength of B-79 in acetone/water solutions of various NaOH concentrations decreased continuously. The hydrolysis rate of B-79 increased with increasing alkali concentration and appeared following first order reaction. The observed rate constants for various concentrations of B-79 showed similar values, and B-79 was hydrolyzed by first order reaction for dye concentration. Therefore, it was confirmed that the overall reaction follow second order kinetics and proceed via S/sub n/2 reaction. From the study on kinetics and spectrometric analysis, it was proposed that the rate determining step of the hydrolysis reaction of B-79 is the nucleophilic substitution reaction - that is the reaction of the rapid attack of $OH^{-}$ on the carbon atom, which is in acceptor ring, adjacent to azo group to break the C-N bond. And it was also found that the final hydrolysis products of B-79 include both the acceptor ring in the form of sodium salt and the donor ring possessing 4-N,N-dihydroxyethyl group converted from 4-N,N-diacetoxyethyl group.

C. I. Disperse Blue 79의 알칼리 가수분해 반응속도 및 반응메카니즘 (Kinetics and Mechanism for Alkaline Hydrolysis of C. I. Disperse Blue 79)

  • 박건용;박창혁;박병기
    • 한국염색가공학회지
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    • 제13권5호
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    • pp.312-319
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    • 2001
  • Kinetics and mechanism for alkaline hydrolysis of C. I. Disperse Blue 79(B-79) which is 4-N, N- diacetoxyethyl -2- acylamino-5-ethos y -2'-bromo-4',6'-dinitroazobenzene were investigated. The color strength of B-79 in acetone/water solutions of various NaOH concentrations decreased continuously. The hydrolysis rate of B-79 increased with increasing alkali concentration and appeared following first order reaction. The observed rate constants for various concentrations of B-79 showed similar values, and B-79 was hydrolyzed by first order reaction for dye concentration. Therefore, it was confirmed that the overall reaction follow second order kinetics and proceed via $S_N2$ reaction. From the study on kinetics and spectrometric analysis, it was proposed that the rate determining step of the hydrolysis reaction of B-79 is the nucleophilic substitution reaction - that is the reaction of the rapid attack of OH- on the carbon atom, which is in acceptor ring, adjacent to auto group to break the C-N bond. And it was also found that the final hydrolysis products of B-79 include both the acceptor ring in the form of sodium salt and the donor ring possessing 4-N,N-dihydroxyethyl group converted from 4-N, N-diacetoxyethyl group.

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Rahnella aquatilis를 이용한 Lactan gum 생산에서 탄수화물 대사

  • 나건;이성호;이기영
    • 한국미생물·생명공학회지
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    • 제24권4호
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    • pp.493-499
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    • 1996
  • Lactan gum produced by Rahnella aquatilis is a high viscous, anionic polysaccharide and has shear thinning behaviour. Lactan gum yield and cencentration was greater on disaccharide such as lactose and sucrose than on monosaccharides such as glucose and galactose. When initial carbon source concentration was 45g/l of sucrose of lactose, the microorgnisms produced 28 g/l and 27 g/l of lactan, respectively with a yield more than 60%. $\beta$-Galactosidase, hydrolyzing lactose into galactose and glucose, was induced by lactose or galactose. When initial corbon source was 45 g/l of mixed carbon I (glucose:galactose=1:1), lactan gum concentaration was higher than that from 45 g/l of monosaccharide (glucose pf galactose) but was similar to the result from 45 g/l of lactose. Therefore, lactose hydrolysis reaction by $\beta$-galactosidase does not seem to be a rate determining step in lactan gum biosynthesis. When initial carbon source was 45 g/l of mixed carbon II (glucose:fructose=1:1). total carbon source consumption rate was slower than that from sucrose, but glucose consumption rate was faster than that from fructose.

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Effect of Nonleaving Group on the Reaction Rate and Mechanism: Aminolyses of 4-Nitrophenyl Acetate, Benzoate and Phenyl Carbonate

  • Um, Ik-Hwan;Park, Hye-Ran;Kim, Eun-Young
    • Bulletin of the Korean Chemical Society
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    • 제24권9호
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    • pp.1251-1255
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    • 2003
  • Second-order rate constants have been determined spectrophotometrically for the reaction of phenyl 4-nitrophenyl carbonate with a series of primary amines in $H_2O$ containing 20 mol % DMSO at 25.0 ${\circ}$C. The Bronsted-type plot is linear with a ${\beta}_{nuc}\;0.69 {\pm} 0.04$, which is slightly smaller than the ${\beta}_{nuc}$ values for the reactions of 4-nitrophenyl acetate ( $\beta_{nuc}= 0.82 {\pm} 0.03$) and benzoate ( $\beta_{nuc} = 0.76 {\pm} 0.01$), indicating that the reaction proceeds through a tetrahedral zwitterionic intermediate $T^{\pm}$. The carbonate is more reactive than the corresponding acetate and benzoate. The changing Me (or Ph) to PhO has resulted in a decrease in the ${\beta}_{nuc}$ value without changing the reaction mechanism but an increase in the reactivity. The electronic effect of the substituent in the nonleaving group appears to be responsible for the enhanced reactivity of the carbonate compared with the corresponding acetate and benzoate.

다단계 퍼지 리스크 그래프 모델을 적용한 SIL 할당에 관한 연구 (A Study of SIL Allocation with a Multi-Phase Fuzzy Risk Graph Model)

  • 양희갑;이종우
    • 한국철도학회논문집
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    • 제19권2호
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    • pp.170-186
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    • 2016
  • 본 논문에서는 철도 시스템에서 안전무결성수준 평가를 위한 다단계 퍼지 리스크 그래프를 제안한다. 본 모델은 입력변수의 모호함과 주관적 전문가 판단의 단점을 보완하는 것을 목적으로 한다. 다단계 퍼지 리스크 그래프 모델은 2단계로 구성된다. 본 논문에서는 첫 번째 퍼지화를 위한 상세 입력 변수가 제안되고 첫 번째 단계에서 퍼지 이론을 적용하여 기존의 리스크 그래프 입력 변수인 심각도, 노출도, 회피도, 요구율을 산정한다. 퍼지 추론 및 역퍼지화 결과 2단계에서 적용할 입력변수가 도출된다. 두 번째 단계에서는 식별된 해당 해저드에 대하여 안전 무결성 수준과 허용 해저드율을 산정하여 안전 요구사항을 수립한다. 또한 다단계 퍼지 리스크 그래프 모델을 검증하기 위해 CENELEC SC 9XA WG A10 보고서에 소개된 건널목 시스템을 대상으로 한 안전성 평가 결과와 비교하여 모델을 검증하였으며, 철도 분야의 초기 개념 설계 단계 안전성 요구사항을 수립 시 적용할 수 있다.