• Title/Summary/Keyword: Basic Values

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Kinetics and Mechanism of the Benzylaminolysis of O,O-Diphenyl S-Aryl Phosphorothioates in Dimethyl Sulfoxide

  • Adhikary, Keshab Kumar;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.5
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    • pp.1625-1629
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    • 2011
  • Kinetic studies of the reactions of O,O-diphenyl Z-S-aryl phosphorothioates with X-benzylamines have been carried out in dimethyl sulfoxide at 55.0 $^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}_X$) and Bronsted [log $k_2$ vs $pK_a(X)$] plots for substituent X variations in the nucleophiles are biphasic concave downwards with a maximum point at X = H, and the unusual positive ${\rho}_X$ and negative ${\beta}_X$ values are obtained for the strongly basic benzylamines. The sign of the cross-interaction constant (${\rho}_{XZ}$) is negative for both the strongly and weakly basic nucleophiles. Greater magnitude of ${\rho}_{XZ}$ value is observed with the weakly basic nucleophiles (${\rho}_{XZ}$ = -2.35) compared to with the strongly basic nucleophiles (${\rho}_{XZ}$ = -0.03). The deuterium kinetic isotope effects ($k_H/k_D$) involving deuterated benzylamines [$XC_6H_4CH_2ND_2$] are primary normal ($k_H/k_D$ > 1). The proposed mechanism is a concerted $S_N2$ involving a frontside nucleophilic attack with a hydrogen bonded, four-center-type transition state for both the strongly and weakly basic nucleophiles. The unusual positive ${\rho}_X$ and negative ${\beta}_X$ values with the strongly basic benzylamines are rationalized by through-space interaction between the ${\pi}$-clouds of the electron-rich phenyl ring of benzylamine and the phenyl ring of the leaving group thiophenoxide.

Electrophoretic pattern and classification of chitinolytic enzymes from Rehmannia glutinosa (지황 chitin 분해효소의 전기영동 양상 및 분류)

  • Pan, Cheol-Ho;Lee, Eun-A;Jo, Do-Hyun;Kim, Su-Il
    • Applied Biological Chemistry
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    • v.41 no.7
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    • pp.505-509
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    • 1998
  • Chitinase, which is one of the pathogenesis-related proteins, was examined from Rehmannia glutinosa. Rehmannia chitinases were classified into basic and acidic groups by chitin affinity column chromatography. According to the chitinase pattern by native PAGE, basic chitinases of low Rf values were extracted more under an acidic condition (pH 2.9) than a basic condition (pH 8.8), while acidic chitinases having high Rf values were mainly detected in basic extracts. There were in total seven chitinase isoforms of three basic and four acidic isoforms in Rehmannia. The range of molecular weight of Rehmannia chitinase was from 28 to 32 kD. It showed the possibility of tissue specific expression of acidic chitinases and basic chitinases were mainly detected in root.

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A DFT Study on the Polarizability of Di-substituted Arene (o-, m-, p-) Molecules used as Supercharging Reagents during Electrospray Ionization Mass Spectrometry

  • Abaye, Daniel A.;Aniagyei, Albert;Adedia, David;Nielsen, Birthe V.;Opoku, Francis
    • Mass Spectrometry Letters
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    • v.13 no.3
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    • pp.49-57
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    • 2022
  • During electrospray ionization mass spectrometry (ESI-MS) analysis of proteins, the addition of supercharging agents allows for adjusting the maximal charge state, affecting the charge state distribution, and increases the number of ions reaching the detector thus, improving signal detection. We postulate that in di-substituted arene isomers, molecules with higher polarizability values should generate greater interactions and hence elicit higher signal intensities. Polarizability is an electronic parameter which has been demonstrated to predict many chemical interactions. Many properties can be predicted based on charge polarization. Molecular polarizability is a vital descriptor for explaining intermolecular interactions. We employed DFT (density functional/Hartree-Fock hybrid model, B3LYP)-derived descriptors and computed molecular polarizability for ten disubstituted arene reagents, each set made up of three (ortho, meta, para) isomers, with reported use as supercharging reagents during ESI experiments. The atomic electronic inputs were ionization potential (IP), electron affinity (EA), electronegativity (𝛘), hardness (η), chemical potential (µ), and dipole moment (D). We determined that the para isomers showed the highest polarizability values in nine of the ten sets. There was no difference between the ortho and meta isomers. Polarizability also increased with increasing complexity of the substituents on the benzene ring. Polarizability correlated positively with IP, EA, 𝛘, η, and D but correlated negatively with chemical potential. This DFT study predicts that the para isomers of di-substituted arene isomers should elicit the strongest ESI responses. An experimental comparison of the three isomers, especially of larger supercharging molecules, could be carried out to establish this premise.

Estimation based on lower record values from exponentiated Pareto distribution

  • Yoon, Sanggyeong;Cho, Youngseuk;Lee, Kyeongjun
    • Journal of the Korean Data and Information Science Society
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    • v.28 no.5
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    • pp.1205-1215
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    • 2017
  • In this paper, we aim to estimate two scale-parameters of exponentiated Pareto distribution (EPD) based on lower record values. Record values arise naturally in many real life applications involving data relating to weather, sport, economics and life testing studies. We calculate the Bayesian estimators for the two parameters of EPD based on lower record values. The Bayes estimators of two parameters for the EPD with lower record values under the squared error loss (SEL), linex loss (LL) and entropy loss (EL) functions are provided. Lindley's approximate method is used to compute these estimators. We compare the Bayesian estimators in the sense of the bias and root mean squared estimates (RMSE).

A Suggestion of the Modified Weighting Values of the RMR Parameters Using a Multiple Regression Analysis on Rock Slopes (암반사면을 대상으로 다변량 수량화 기법을 응용한 RMR 인자의 수정 가중치 제안)

  • Chae Byung-Gon;Kim Kwang-Sik;Cho Yong-Chan;Seo Yong-Seok
    • The Journal of Engineering Geology
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    • v.16 no.1 s.47
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    • pp.85-96
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    • 2006
  • This study was conducted to suggest a method to determine weighting values of each parameter of the RMR system considered with geologic characteristics of a study area. This study reviewed the weighting values of the RMR system for the Cretaceous sedimentary rocks distributed in Ulsan area. Based on the data of field survey at the study area, a multiple regression analysis was used to set up an optimal weighting values of the RMR parameters. For the multiple regression analysis, each parameter of the RMR and the slope gradient were regarded as the independent variable and the dependent variable, respectively. The analysis result suggested a modified weighting values of the RMR parameters as follows; 30 for the intact strength of rock; 18 for RQD; 8 for spacing of discontinuities; 32 for the condition of discontinuities; and 12 for ground water.

A Study of Pattern Making of Dooroomaky by Computer (컴퓨터에 의한 한복 여자 두루마기 원형제도에 관한 연구)

  • Kim Hee Sook
    • Journal of the Korean Society of Clothing and Textiles
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    • v.12 no.3 s.28
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    • pp.319-331
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    • 1988
  • The purpose of this study was to develop a computer program for pattern making of women's Dooroomaky. The following results were given through utilizing the Computer in pattern making of Dooroomaky for women. 1. Computerization of the pattern making process was expected to provide higher accuracy and efficiency in pattern making. 2. Basic pattern was drafted by the hand-operation. In this study, this Dooroomaky basic pattern was selected. And a computer program for drafting was developed. Refer to

    1. 3. Basic points which can be connected to depict basic pattern are represented with the numerical expression and the curved lines consist of the types of Arc Command. 4. In order to draft straight lines of the basic pattern, relative co-ordinate values of all standard points were prescrived and each two standard points were connected in straight lines respectively. 5. The patterns of Dooroomaky were automatically depicted by inputting the standard size (large, medium and small) find body measurement for pattern(bust girth, center back length, sleeve length, Dooroomaky length). 6. Grading of standard size was accomplished by using same method.

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  • Development of Method for Deciding Automatically Parameters of Water Quality Simulation Models (수질모형의 매개변수 자동보정 프로그램 개발에 관한 연구)

    • Song, Kwang-Duck;Paik, Do Hyeon;Lee, Yong Woon
      • Journal of Environmental Impact Assessment
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      • v.15 no.2
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      • pp.101-109
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      • 2006
    • Water quality simulation models include the difference between the measured and estimated values as an inevitable consequence because they represent the complicated natural phenomena as simplified mathematical equations. The major reason of the difference occurrence is due to the use of the imprecise values of the model parameters, but the parameter values are currently determined by the try and error method directly performed by humans. However, the use of this method requires many time and endeavor of humans, and generally does not obtain the most suitable parameter values. A method for deciding model parameter values is, therefore, developed in this study. The method minimizes the difference between the measured and estimated values and also distributes uniformly the measured values on the upper and lower sides of the line representing the estimated values. A user interface based on this method is also developed by using the Visual Basic 6.0 of Microsoft, and it can be operated in the environment of Windows 98/2000. In this study, the method for deciding model parameter values is applied for estimating the water quality of the stream Ko-heung. The results of the application show that the method, including its computer program, can effectively obtain the most suitable parameter values and also save many working time in comparison with the existing method directly performed by humans.

    Kinetics and Mechanism of the Pyridinolysis of Methyl Phenyl Phosphinic Chloride in Acetonitrile

    • Adhikary, Keshab Kumar;Lee, Hai-Whang
      • Bulletin of the Korean Chemical Society
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      • v.32 no.6
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      • pp.1945-1950
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      • 2011
    • The pyridinolysis of methyl phenyl phosphinic chloride is investigated kinetically in acetonitrile at -20.0 $^{\circ}C$. The Hammett and Br${\o}$nsted plots for substituent X variations in the nucleophiles are biphasic concave downwards with a break point at X = H, and unusual positive ${\rho}_X$ (= 2.94) and negative ${\beta}_X$ (= -0.48) values are obtained for the strongly basic nucleophiles. A stepwise mechanism with a rate-limiting step change from bond breaking for the weakly basic pyridines to bond formation for the strongly basic pyridines is proposed on the basis of biphasic concave downward Hammett and Br${\o}$nsted plots. Unusual positive ${\rho}_X$ and negative ${\beta}_X$ values are rationalized by the isokinetic relationship. The pyridinolyses and anilinolyses of four $R_1R_2$P(=O)Cl-type substrates, dimethyl, diethyl, methyl phenyl, and diphenyl phosphinic chlorides in acetonitrile are compared to obtain systematic information on phosphoryl transfer reaction mechanism. The combination of the two ligands, Me and Ph, shows unexpected kinetic results for both the anilinolysis and pyridinolysis: greatest magnitude of $k_H/k_D$ (= 2.10) involving deuterated anilines $[XC_6H_4NH_2(D_2)]$ for the anilinolysis, and exceptionally fast rate and biphasic concave downward free energy correlation for the pyridinolysis.

    Study on the Large Scale Solar Thermal Power Plant System by Using the TRNSYS Program (TRNSYS를 이용한 대규모 태양열발전시스템 성능 연구)

    • Kim, Jong-Kyu;Kang, Yong-Heack;Kim, Jin-Su;Lee, Sang-Nam;Yu, Chang-Kyun;Yun, Hwan-Ki
      • 한국신재생에너지학회:학술대회논문집
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      • 2006.11a
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      • pp.176-179
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      • 2006
    • This paper describes the procedure of the basic design and transient variation of performance for a 1MWe large scale solar thermal power plant system (STPPS) by using the commercial software tool of TRNSYS. In order to simulate the transient variation of STPPS's performance, the basic design of STPPS are preceded by using the THERMOFLEX, Three different days of DNI weather data of Daejeon in 2005 are used to calculate the performance. For a high DNI data values, the general ing power of 1.1 MWe and flow rate of 1.4kg/s at $804W/m^2$ are good agreement with the basic design value of 1.0 MWe, 1.36 kg/s at $800 /m^2$. Using the other weather data of low and sudden decreasing DNI values, the results show that the output power and flow rate follow well the DNI variation. Based on the results, it is allowed to use the Program to estimate the performance of STPPS for variety of DNI data.

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    A PROPOSAL OF CONSTRUCTABILITY REVIEW IN THE BASIC DESIGN STEP FOR DESIGN-BUILD PROJECTS

    • Sung-Wook Choi;Young-Woong Song;Yoon-Ki Choi;Dong-Woo Shin;Jae-Youl Chun
      • International conference on construction engineering and project management
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      • 2005.10a
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      • pp.1150-1153
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      • 2005
    • The orders of Design-Build Delivery System (DBDS) in a large and public construction project have been increasing. Single Source Responsibility (SSR) for design and construction, which contributes to quality improvement of design and construction, has been performed. The DBDS performs SSR for design and construction, but, it has not maximized effect because of the dissatisfied alternative analysis procedures which are based on constructability evaluation and the information system in the design step. In this research, Constructability Evaluation Factors (CEFs) that must be evaluated, investigated, and reflected in the basic design step for design-build projects. The CEF proposed and the business process of each conductor has been systematized. To propose constructability evaluation factors, first classify drawing information by the constructability evaluation sphere. CEFs must be proposed to evaluate factors according to interference among work items. Second, applicable CEFs must be classified by preference ranking and weight. Third, the values of constructability factors in accordance with building elements and work items, need to be calculated. Finally, the CEFs proposal will support rational decision making, design cost reduction, and quality improvement through the values for constructability of building elements and work items.

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