Chemometric Analysis of Substituent Effects. IX. Alternative Interpretation of Substituent Effects (AISE) - Orthogonal Model

1996 ◽  
Vol 61 (5) ◽  
pp. 704-712 ◽  
Author(s):  
Oldřich Pytela
Keyword(s):  
Gas Phase ◽  
Substituent Effects ◽  
Alternative Interpretation ◽  
Reaction Centre ◽  
Class Iii ◽  
Coordinate Axis ◽  
The Family ◽  
Reaction Constants ◽  
The Individual ◽  
Point Of Intersection

Continuing the previous communications, the present paper suggests an orthogonal model of alternative interpretation of substituent effects (AISE). Following this approach, substituents are classified into three classes. Those of class II are defined as substituents whose atom bound to the basic skeleton bears a character of nucleophile, i.e. it is able of an intramolecular nucleophilic interaction with the reaction centre. The class III includes substituents whose atom bound to the basic skeleton is electrophilic in nature and can correspondingly interact with the reaction centre too. The class I includes the substituents possessing none of the above-mentioned characteristics. Within the model suggested the substituent effects can be described by a family of three lines corresponding to the substituent classes described with a single substituent constant at the coordinate axis. The validity of the model suggested has successfully been tested by comparison with other correlation equations using 318 reaction series taken from literature. It has been found that the value of the point of intersection at the coordinate axis (the isosubstituent constant) is smaller in processes with electron deficit and grater in those with electron excess in the reaction centre. The slopes of the individual lines in the family of lines (the reaction constants) decrease in the order II > I > III in most cases, the only exception being the processes with direct conjugation between a negatively charged reaction centre and the substituent and some gas phase processes.

Chemometric Analysis of Substituent Effects. VIII. Alternative Interpretation of Substituent Effects (AISE)

1995 ◽  
Vol 60 (9) ◽  
pp. 1502-1528 ◽  
Author(s):  
Oldřich Pytela
Keyword(s):  
Multiple Bond ◽  
Substituent Effects ◽  
Alternative Interpretation ◽  
Class I ◽  
Reaction Centre ◽  
Correlation Equations ◽  
Class Iii ◽  
Substituent Constant ◽  
Chemical Models ◽  
The Individual

Alternative interpretation of substituent effects (AISE) starts from the presumption that a substituent only possesses a single property described by a single substituent constant. This property is transmitted to the reaction centre by three different ways depending on the interaction type in the triad reaction centre - basic skeleton - substituent. For interpretation it is substantial whether or not the substituent has p electrons at the atom adjacent to the basic skeleton. If it has none, the substituent belongs to class I and operates only by its basic effect described by the mentioned single substituent constant. Substituents of class II possess a free electron pair at the atom adjacent to the basic skeleton, and those of class III have a multiple bond between the first and the second atoms which is polarized in the direction from the basic skeleton. Substituent effects in class I are described by a substituent constant identical with σI constant. Substituents in classes II and III show additional effects proportional to the same constant. Hence, a separate treatment of substituent effects in the individual classes provides three straight lines intersecting in a common point. Mathematically, the description of substituent effects in this approach is expressed by a family of lines with a single explaining variable. The point of intersection, which is referred to as the iso-effect point, is not identical with the classic standard substituent - hydrogen - but is near to CN substituent. The approach given has the advantage of adopting a single substituent constant whose scale can be adjusted relatively precisely. Its drawback (like in the case of the correlation equations derived from the principle of separation of substituent effects) lies in a more extensive set of substituents needed for a correlation. The AISE principle has been applied to 318 series of experimental data describing effects of 32 substituents in a large variety of chemical models (aliphatic, alicyclic, aromatic, heteroaromatic, with or without direct conjugation between reaction centre and substituent) in both chemical reactions and equilibria. A comparison with two other correlation relations with two and three substituent constants for interpretation of substituent effects based on the principle of separation of the individual substituent effects showed that the closeness of AISE based correlations is comparable with that of the correlation equations currently used. It was somewhat less successful in the models with direct conjugation between reaction centre and substituent but the AISE principle can be used even in these cases.

Analysis of substituent and solvent effects on dissociation of N-phenylbenzenesulphonamides

1987 ◽  
Vol 52 (12) ◽  
pp. 2900-2908 ◽  
Author(s):  
Miroslav Ludwig ◽  
Oldřich Pytela ◽  
Helena Javůrková ◽  
Miroslav Večeřa
Keyword(s):  
Factor Analysis ◽  
Hydrogen Bonds ◽  
Model Equation ◽  
Substituent Effects ◽  
Regression Function ◽  
Reaction Centre ◽  
Solvent Dependence ◽  
Substituent Constants ◽  
Reaction Constants

The potentiometric titration in water, methanol, dimethyl sulphoxide, dimethylformamide, and acetonitrile has been used for determination of pK values of 13 N-arylbenzenesulphonamides. The validity of the Hammett and Yukawa-Tsuno models using several sets of substituent constants has been evaluated by the test to check adequacy of the regression function and by the factor analysis. It has been found that the substituent effects in solvents must be interpreted with regard to the experimental method used, solvent, set of the substituent constants, as well as the model equation ETR. The dependence of the Hammett reaction constants on the solvent has been analyzed and reveals a preferred stabilization of the conjugated base through hydrogen bonds. Direct conjugation of the reaction centre with the substituent and with different extent of the solvent-dependence with the 4-CN and 4-NO2 derivatives have been observed.

Ortho Effect in Dissociation of Benzoic Acids with Electron-Accceptor Substituents Using the AISE Theory; Relation to para Substitution and Solvent

2002 ◽  
Vol 67 (5) ◽  
pp. 596-608 ◽  
Author(s):  
Oldřich Pytela ◽  
Jiří Kulhánek
Keyword(s):  
Electron Acceptor ◽  
Dissociation Constants ◽  
Electrostatic Force ◽  
Substituent Effects ◽  
Alternative Interpretation ◽  
Ring Closure ◽  
Reaction Centre ◽  
Benzoic Acids ◽  
Carboxylate Group ◽  
The Given

Potentiometric titration at 25 °C has been used to measure the dissociation constants of 2- and 4-substituted benzoic acids with electron-acceptor substituents in methanol, N,N-dimethylformamide, acetonitrile, and acetone. But for a few exceptions, no significant differences have been found between the dissociation constants measured and those given in literature. Using the measured pKa values, those of 3-substituted derivatives taken from literature (measured in the same solvents) and those of 3- and 4-substituted derivatives measured in water, the so far missing substituent constants σi of NO and CH3SO substituents have been determined by Alternative Interpretation of Substituent Effects (AISE). The previously published relationships and the σi constants have been used to calculate the σm and σp constants for the given substituents and compare them with literature. The agreement was the better, the more reliable the corresponding Hammett substituent constant was. Using a non-linear regression model, we have analysed the structure of matrix of pKa values of ten 2-X-benzoic acids (X is electron-acceptor substituent) measured in the given organic solvents and in water. It has been found that in non-aqueous solvents the conjugate base of benzoic acid is stabilised by intramolecular hydrogen bond if X is COOH and SO2NH2 or electrostatic force if X is CH3SO. On the other hand, in water the carboxylate group is out of the plane of the benzene ring due to interaction between the solvated reaction centre and substituent, this being the case with all the substituents except for X = CHO, CH3CO, NO, and CN. In all the solvents used, intramolecular ring closure takes place between the carboxylate group and substituent X = CH3CO, CHO, and NO, this phenomenon being the most important in water.

Analysis of Substituent Effects in Naphthalene Skeleton

2004 ◽  
Vol 69 (12) ◽  
pp. 2297-2314
Author(s):  
Patrik Pařík ◽  
Miroslav Ludwig
Keyword(s):  
Dissociation Constants ◽  
Comprehensive Evaluation ◽  
Substituent Effects ◽  
Principal Component ◽  
Alternative Interpretation ◽  
Point Of View ◽  
Carboxylic Group ◽  
Resonance Effects ◽  
The Individual

The dissociation constants of 45 substituted 1- and 2-naphthoic acids in six organic solvents (methanol, ethanol, acetonitrile, dimethylformamide, dimethyl sulfoxide, pyridine) have been used to evaluate the substituent effects in the naphthalene skeleton. The dissociation constants data have been treated traditionally by using Dewar-Grisdale equation and the Taft DSP equation, and the alternative interpretation of substituent effects (AISE) method. Quantitative comparison of substituent effects and their transmission from different positions, combination of inductive and resonance effects from various positions, and effects of solvents are discussed. Best results are predominantly provided by the AISE. Substituent effects are stronger in the case of substituents affecting from ring of the naphthalene skeleton bearing carboxylic group than from ring not bearing carboxylic group, and there are no substantial differences between the individual positions of this ring. The contribution of resonance effects at 4α and 8β positions distinctly changes with the medium. Special quality of substituent H was found in comparison with other substituents presumably due their bulkier character. The principal component analysis (PCA) has been also applied to treat the mean dissociation constants using the single substituent property approach. The dissociation together with reactivity data for other naphthalene derivatives have been tested for comprehensive evaluation using PCA. There was found a large similarity of naphthalene reactivity data tested from the point of view of substituent effects.

Reactivity of p-Substituted Benzaldoximes in the Cleavage of p-Nitrophenyl Acetate: Kinetics and Mechanism

2004 ◽  
Vol 69 (2) ◽  
pp. 397-413 ◽  
Author(s):  
Jan Pícha ◽  
Radek Cibulka ◽  
František Hampl ◽  
František Liška ◽  
Patrik Pařík ◽  
...  
Keyword(s):  
Dissociation Constants ◽  
Substituent Effects ◽  
Statistical Modelling ◽  
Reaction Centre ◽  
Deprotonated Form ◽  
Rate Limiting Step ◽  
Reaction Constant ◽  
Reaction Constants ◽  
Intramolecular Hydrogen ◽  
The Given

Eleven p-substituted benzaldoximes (p-XC6H4CH=NOH, where X = H, CH3, CF3, F, Cl, Br, OCH3, N(CH3)2, COOCH3, CN, NO2) have been synthesized and their dissociation constants determined in 10% (v/v) aqueous dioxane at 35 °C. Under the same conditions, the pseudo-first order rate constants kobs of their reactions with p-nitrophenyl acetate (PNPA) were measured at pH values from 7.8 to 10.8 and at concentrations coxime ranging from 0 to 4.00 × 10-3 mol l-1. The kinetic model and mechanism of the said reaction was proposed by means of mathematical statistical modelling of the dependences of kobs on pH and coxime. The mechanism involves a pre-equilibrium (k-1/k1) in which PNPA forms a tetrahedral intermediate (THI) with the deprotonated form of oxime. In the given medium, THI is in equilibrium with the non-reactive conjugated acid THIH (dissociation constant Ka,THIH) which is stabilized by intramolecular hydrogen bond. Depending on pH, the rate-limiting step consists either in formation of THI from educts (pH < pKa,oxime) or in its spontaneous (k2) and oxime-catalyzed (k3, general acid catalysis) decomposition to products (pH > pKa,oxime). Evaluation of substituent effects on dissociation constants (Ka,oxime) of the oximes showed that there is no direct conjugation between the substituent and the reaction centre (the found reaction constant ρ(Ka,oxime) = 0.91). The transmission coefficient of the transfer of these effects through C=N-O grouping corresponds approximately to one bond. The reaction constants in the Hammett equation obtained from the regression model are: ρ(k-1Ka,THIH/k1) = 1.29, ρ(k2Ka,THIH) = 0.20 and ρ(k3Ka,THIH) = 0.67. These reaction constants have been discussed with the regard to the reaction mechanism suggested.

Effect of amiodarone on heart rate variability in patients with newly diagnosed atrial fibrillation (clinical observation)

2020 ◽  
pp. 81-85
Author(s):  
E. P. Popova ◽  
O. T. Bogova ◽  
S. N. Puzin ◽  
D. A. Sychyov ◽  
V. P. Fisenko
Keyword(s):  
Atrial Fibrillation ◽  
Heart Rate ◽  
Heart Rate Variability ◽  
Drug Therapy ◽  
Heart Function ◽  
Newly Diagnosed ◽  
Class Iii ◽  
Spectral Parameters ◽  
Patient Will ◽  
The Individual

Spectral analysis of heart rate variability gives an idea of the role of the autonomic nervous system in the regulation of chronotropic heart function. This method can be used to evaluate the effectiveness of drug therapy. Drug therapy should be carried out taking into account the individual clinical form of atrial fibrillation. Information about the vegetative status of the patient will undoubtedly increase the effectiveness of treatment. In this study, spectral parameters were studied in patients with newly diagnosed atrial fibrillation. The effect of antiarrhythmic drug class III amiodarone on the spectral parameters of heart rate variability was studied.

VALUE EDUCATION SYSTEM IN INDIA

2019 ◽  
Vol 8 (1) ◽  
Author(s):  
Jyoti Narayan Patra ◽  
Jayanta Mete
Keyword(s):  
Education System ◽  
Personality Development ◽  
The Family ◽  
The Individual ◽  
The Right

Values are like seeds that sprout, become saplings, grow into trees and spread their branches all around. To be able to think right, to feel the right kind of emotions and to act in the desirable manner are the prime phases of personality development. Building up of values system starts with the individual, moves on to the family and community, reorienting systems, structures and institutions, spreading throughout the land and ultimately embracing the planet as a whole. The culture of inclusivity is particularly relevant and important in the context of our society, nation and making education a right for all children.

THE VALUE OF LOVE IN THE SYSTEM OF FORMATION OF THE PROFESSIONAL MATURITY OF THE EDUCATOR

2020 ◽  
Vol 1 (10(79)) ◽  
pp. 12-18
Author(s):  
G. Bubyreva
Keyword(s):  
Russian Federation ◽  
The State ◽  
Educational Process ◽  
Wide Range ◽  
The Family ◽  
The Russian Federation ◽  
The Government ◽  
The Individual ◽  
The Right

The existing legislation determines the education as "an integral and focused process of teaching and upbringing, which represents a socially important value and shall be implemented so as to meet the interests of the individual, the family, the society and the state". However, even in this part, the meaning of the notion ‘socially significant benefit is not specified and allows for a wide range of interpretation [2]. Yet the more inconcrete is the answer to the question – "who and how should determine the interests of the individual, the family and even the state?" The national doctrine of education in the Russian Federation, which determined the goals of teaching and upbringing, the ways to attain them by means of the state policy regulating the field of education, the target achievements of the development of the educational system for the period up to 2025, approved by the Decree of the Government of the Russian Federation of October 4, 2000 #751, was abrogated by the Decree of the Government of the Russian Federation of March 29, 2014 #245 [7]. The new doctrine has not been developed so far. The RAE Academician A.B. Khutorsky believes that the absence of the national doctrine of education presents a threat to national security and a violation of the right of citizens to quality education. Accordingly, the teacher has to solve the problem of achieving the harmony of interests of the individual, the family, the society and the government on their own, which, however, judging by the officially published results, is the task that exceeds the abilities of the participants of the educational process.  The particular concern about the results of the patriotic upbringing served as a basis for the legislative initiative of the RF President V. V. Putin, who introduced the project of an amendment to the Law of RF "About Education of the Russian Federation" to the State Duma in 2020, regarding the quality of patriotic upbringing [3]. Patriotism, considered by the President of RF V. V. Putin as the only possible idea to unite the nation is "THE FEELING OF LOVE OF THE MOTHERLAND" and the readiness for every sacrifice and heroic deed for the sake of the interests of your Motherland. However, the practicing educators experience shortfalls in efficient methodologies of patriotic upbringing, which should let them bring up citizens, loving their Motherland more than themselves. The article is dedicated to solution to this problem based on the Value-sense paradigm of upbringing educational dynasty of the Kurbatovs [15].

CHILD-PARENT RELATIONS AS A FACTOR IN THE FORMATION OF PROFESSIONAL PREFERENCES IN PEDAGOGICAL DYNASTIES

2020 ◽  
Vol 2 (4) ◽  
pp. 126-130
Author(s):  
N. V. SHAMANIN ◽  
Keyword(s):  
Professional Development ◽  
The Family ◽  
The Individual ◽  
Relationship Of ◽  
The Relationship ◽  
Parent Child Relationships ◽  
Professional Preferences ◽  
Parent Child

The article raises the issue of the relationship of parent-child relationships and professional preferences in pedagogical dynasties. Particular attention is paid to the role of the family in the professional development of the individual. It has been suggested that there is a relationship between parent-child relationships and professional preferences.

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