University Sétif 1 FERHAT ABBAS Faculty of Sciences
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Auteur Douniazed HANNACHI |
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Ajouter le résultat dans votre panier Affiner la rechercheQuantum Chemical Investigation for Exploring the Antioxidant Activity of Thiaflavan Compounds / Nour el houda AMRANE
Titre : Quantum Chemical Investigation for Exploring the Antioxidant Activity of Thiaflavan Compounds Type de document : texte imprimé Auteurs : Nour el houda AMRANE, Auteur ; Douniazed HANNACHI, Directeur de thèse Editeur : Setif:UFA Année de publication : 2019 Importance : 1 vol (60 f.) Format : 29 Langues : Anglais (eng) Catégories : Thèses & Mémoires:Chimie Mots-clés : Quantum
Chemical Investigation
Antioxidant Activity
Thiaflavan
CompoundsRésumé : Conclusion
In this work, for the first time the antioxidative properties of thiaflavan and
thiaflavan-ferrocene in the gas, water and benzene phases were studied from
theoretical aspect.
The calculated molecular properties (chemical potential, hardness and
electrophilicity index) of DNA and thiaflavan compounds clearly confirm that the
thiaflavan mostly act as electron donners in their interaction with the DNA. Our
results showing that the thymine moiety in DNA is the primary target for the
thiaflavan drugs.
Based on the above result, three main antioxidant mechanisms, namely HAT,
SET-PT and SPLET were taken into account to analyze the antioxidative capacity
of thiaflavan compounds in the gas, water and benzene phases.
As for the HAT mechanism, from the magnitude of the lowest BDE values, in the
gas and solvent the two successive hydroxyl groups in the A or B ring (3- 4-
position in the A ring and 1-2- position in the B ring) have higher H-atom donation
ability than the single hydroxyl groups in A or in B ring. Our result indicates that
hydroxyl groups at A ring play the key role in scavenging radicals and exhibiting
antioxidant effectiveness.
As for SET-PT mechanism, in the studied environments, the antioxidant activity of
the investigated compounds reveal that PDE values of T13 to T15 (ferrocene
moiety at ring B) are higher than all the thiaflavans compounds.
In SPLET mechanism, in the in the studied medium, from the PA of the
investigated compounds can conclude that the rings B and C’ shows a strong
activity antioxidant than the all cases.
48
We can conclude that the HAT mechanism is the most favorable that the SPLET
and SET-PT.
From the calculated results, OH groups in A-ring contribute mainly to the
antioxidative activities of compared with B-ring. On the other hand, in thiaflavan,
the R3-dihydroxyl groups in ring A are the active site for trapping radicals than the
R4-dihydroxyl.
Our DFT calculations reveal that the better antioxidant is T25’ which have:
two successive hydroxyl groups in the A-ring (3 and 4- position), C'-ring and
ferrocene moiety at ring B.
This work provides an impetus and a benchmark to outlook experiments, for
a determination of the detailed properties of T25’and this compound being
attractive object for future studies of antioxidant properties.Note de contenu : Table of Contents
Abbreviations 3
Introduction 4
Reference 6
Chapter 1 :
Part I: Density Functional Theory
I.1. principals of modern theoretical chemistry 8
I.1.1. Introduction of DFT into chemistry 8
I.1.2. DFT work in the coordination chemistry lab 8
I.1.2.1.CAPABILITIES OF DFT 8
I.2. Theorical Basics of DFT 9
I.3.DFT tools available (Exchange Correlation Functional) 11
I.3.1. LOCAL DENSITY APPROXIMATION: 11
I.3.2.GENERALIZED-GRADIENT APPROXIMATION (GGA) 11
I.3.3.META-GGA DFS 12
I.3.4.HYBRID DFS 12
I.4.Jacob’s ladder 13
I.5. Gaussian bases 14
I.5.1. Polarization function 14
I.5.2. Diffuse function 15
Reference 16
Part II: Flavonoid
II .1. FLAVONOID DERIVATIVES 20
II.1.1. Introduction 20
II.1.2. Generalities about flavonoids 21
II.2. DNA 23
II.3. Antioxidant Activity 24
II.3.1. Methodology for the measurement of Antioxydant capacity 24
ORAC method 24
DPPH method 24
ABTS method 24
FRAP method 25
Reference 26
Chapter 2:
Results and discussion
1. Antioxidant reactions 29
2 .Thiaflavan 30
3.Ferrocene 32
4. Theory and computational details 32
4.1Theory 32
4.2. Computational details 33
5.Results and discussion 35
5.1 Reactivity 35
5 5. 2.Antioxidant activity 38
5. 2.1.The ionization potential 38
5. 2.1.Proton Affinities 41
5. 2.3.Bond dissociation enthalpy 41
5. 2.4.Proton Dissociation Enthalpies 42
5.5.Electron transfer enthalpy 43
5. 5.2.6.Spin density
5- 2. 7 Design of best thiaflavan antioxidant 44
Conclusion 47
Reference 49
Supporting informationCôte titre : MACH/0098 En ligne : https://drive.google.com/file/d/1vqe-1-161CF2r-SAsDraR35qOPX1y9A5/view?usp=shari [...] Format de la ressource électronique : Quantum Chemical Investigation for Exploring the Antioxidant Activity of Thiaflavan Compounds [texte imprimé] / Nour el houda AMRANE, Auteur ; Douniazed HANNACHI, Directeur de thèse . - [S.l.] : Setif:UFA, 2019 . - 1 vol (60 f.) ; 29.
Langues : Anglais (eng)
Catégories : Thèses & Mémoires:Chimie Mots-clés : Quantum
Chemical Investigation
Antioxidant Activity
Thiaflavan
CompoundsRésumé : Conclusion
In this work, for the first time the antioxidative properties of thiaflavan and
thiaflavan-ferrocene in the gas, water and benzene phases were studied from
theoretical aspect.
The calculated molecular properties (chemical potential, hardness and
electrophilicity index) of DNA and thiaflavan compounds clearly confirm that the
thiaflavan mostly act as electron donners in their interaction with the DNA. Our
results showing that the thymine moiety in DNA is the primary target for the
thiaflavan drugs.
Based on the above result, three main antioxidant mechanisms, namely HAT,
SET-PT and SPLET were taken into account to analyze the antioxidative capacity
of thiaflavan compounds in the gas, water and benzene phases.
As for the HAT mechanism, from the magnitude of the lowest BDE values, in the
gas and solvent the two successive hydroxyl groups in the A or B ring (3- 4-
position in the A ring and 1-2- position in the B ring) have higher H-atom donation
ability than the single hydroxyl groups in A or in B ring. Our result indicates that
hydroxyl groups at A ring play the key role in scavenging radicals and exhibiting
antioxidant effectiveness.
As for SET-PT mechanism, in the studied environments, the antioxidant activity of
the investigated compounds reveal that PDE values of T13 to T15 (ferrocene
moiety at ring B) are higher than all the thiaflavans compounds.
In SPLET mechanism, in the in the studied medium, from the PA of the
investigated compounds can conclude that the rings B and C’ shows a strong
activity antioxidant than the all cases.
48
We can conclude that the HAT mechanism is the most favorable that the SPLET
and SET-PT.
From the calculated results, OH groups in A-ring contribute mainly to the
antioxidative activities of compared with B-ring. On the other hand, in thiaflavan,
the R3-dihydroxyl groups in ring A are the active site for trapping radicals than the
R4-dihydroxyl.
Our DFT calculations reveal that the better antioxidant is T25’ which have:
two successive hydroxyl groups in the A-ring (3 and 4- position), C'-ring and
ferrocene moiety at ring B.
This work provides an impetus and a benchmark to outlook experiments, for
a determination of the detailed properties of T25’and this compound being
attractive object for future studies of antioxidant properties.Note de contenu : Table of Contents
Abbreviations 3
Introduction 4
Reference 6
Chapter 1 :
Part I: Density Functional Theory
I.1. principals of modern theoretical chemistry 8
I.1.1. Introduction of DFT into chemistry 8
I.1.2. DFT work in the coordination chemistry lab 8
I.1.2.1.CAPABILITIES OF DFT 8
I.2. Theorical Basics of DFT 9
I.3.DFT tools available (Exchange Correlation Functional) 11
I.3.1. LOCAL DENSITY APPROXIMATION: 11
I.3.2.GENERALIZED-GRADIENT APPROXIMATION (GGA) 11
I.3.3.META-GGA DFS 12
I.3.4.HYBRID DFS 12
I.4.Jacob’s ladder 13
I.5. Gaussian bases 14
I.5.1. Polarization function 14
I.5.2. Diffuse function 15
Reference 16
Part II: Flavonoid
II .1. FLAVONOID DERIVATIVES 20
II.1.1. Introduction 20
II.1.2. Generalities about flavonoids 21
II.2. DNA 23
II.3. Antioxidant Activity 24
II.3.1. Methodology for the measurement of Antioxydant capacity 24
ORAC method 24
DPPH method 24
ABTS method 24
FRAP method 25
Reference 26
Chapter 2:
Results and discussion
1. Antioxidant reactions 29
2 .Thiaflavan 30
3.Ferrocene 32
4. Theory and computational details 32
4.1Theory 32
4.2. Computational details 33
5.Results and discussion 35
5.1 Reactivity 35
5 5. 2.Antioxidant activity 38
5. 2.1.The ionization potential 38
5. 2.1.Proton Affinities 41
5. 2.3.Bond dissociation enthalpy 41
5. 2.4.Proton Dissociation Enthalpies 42
5.5.Electron transfer enthalpy 43
5. 5.2.6.Spin density
5- 2. 7 Design of best thiaflavan antioxidant 44
Conclusion 47
Reference 49
Supporting informationCôte titre : MACH/0098 En ligne : https://drive.google.com/file/d/1vqe-1-161CF2r-SAsDraR35qOPX1y9A5/view?usp=shari [...] Format de la ressource électronique : Exemplaires (1)
Code-barres Cote Support Localisation Section Disponibilité MACH/0098 MACH/0098 Mémoire Bibliothéque des sciences Anglais Disponible
Disponible
Titre : Structural, chemical reactivity, optical and nonlinear Optical properties of Ln (TPH2)2 where ln =La, Pr, Sm, Eu, Gd, Dy, Tm, Yb and lu : DFT + TDDFT study Type de document : texte imprimé Auteurs : Khireddine, ahlem ; Douniazed HANNACHI, Directeur de thèse Editeur : Setif:UFA Année de publication : 2016 Importance : 1vol. (48f.) Format : 30cm. Catégories : Thèses & Mémoires:Chimie Mots-clés : structural,chemical,reactivity,optical,nonlinear optical,Ln(Tp) Résumé :
Conclusion
The present study on Ln(TpH2)2 lanthanide complexes is carried out to understand their structure, reactivity, optical properties and nonlinear optical (NLO) response and further to find correlation between these parameters.
The DFT quantum calculation shows that the Ln(TpH2)2 complexes possess trigonal antiprismatic isostructural (sandwich-like) linear and bent structures. The good correlation between the inter-triangular separation (h Å) and the volume (V Å3) of sandwich-like linear structure.
The calculation of global and local reactivity indices indicates that Eu(TpH2)2 is harder and less reactivethan all complexes and the lanthanide atom is an electron donating site only the Yb, respectively.
The differences between both structures confirmed by the (QTAIM) topological study that there are twohydrogen bonds and two cages in the bent structure, and completely missing in linear sandwich-likestructures.
For the first time, our results demonstrating that the NLO activity enhancement is more related to the direct contribution of 5Note de contenu :
Table of content
Abstract
2
Acknowledgments
4
Table of contents
6
1- Introduction
7
2- Computational method
9
3- Reactivity
10
3-1 Global Reactivity indices
10
3-2 Local Reactivity
11
4- Nonlinear optical
11
5- Results and discussion
13
5-1 Complex structures
13
5-2 Reactivity
15
5-3 Polarizability and first hyperpolarizability
17
5-4 Effect of solvent
19
5-5 The frontier Molecular orbital analysis
21
5-6 TDDFT
22
5-7 Topological study of electron density: QTAIM analysis
24
6- Conclusion
28
7- References
30
8- Supporting information
35Côte titre : MACH/0041 Structural, chemical reactivity, optical and nonlinear Optical properties of Ln (TPH2)2 where ln =La, Pr, Sm, Eu, Gd, Dy, Tm, Yb and lu : DFT + TDDFT study [texte imprimé] / Khireddine, ahlem ; Douniazed HANNACHI, Directeur de thèse . - [S.l.] : Setif:UFA, 2016 . - 1vol. (48f.) ; 30cm.
Catégories : Thèses & Mémoires:Chimie Mots-clés : structural,chemical,reactivity,optical,nonlinear optical,Ln(Tp) Résumé :
Conclusion
The present study on Ln(TpH2)2 lanthanide complexes is carried out to understand their structure, reactivity, optical properties and nonlinear optical (NLO) response and further to find correlation between these parameters.
The DFT quantum calculation shows that the Ln(TpH2)2 complexes possess trigonal antiprismatic isostructural (sandwich-like) linear and bent structures. The good correlation between the inter-triangular separation (h Å) and the volume (V Å3) of sandwich-like linear structure.
The calculation of global and local reactivity indices indicates that Eu(TpH2)2 is harder and less reactivethan all complexes and the lanthanide atom is an electron donating site only the Yb, respectively.
The differences between both structures confirmed by the (QTAIM) topological study that there are twohydrogen bonds and two cages in the bent structure, and completely missing in linear sandwich-likestructures.
For the first time, our results demonstrating that the NLO activity enhancement is more related to the direct contribution of 5Note de contenu :
Table of content
Abstract
2
Acknowledgments
4
Table of contents
6
1- Introduction
7
2- Computational method
9
3- Reactivity
10
3-1 Global Reactivity indices
10
3-2 Local Reactivity
11
4- Nonlinear optical
11
5- Results and discussion
13
5-1 Complex structures
13
5-2 Reactivity
15
5-3 Polarizability and first hyperpolarizability
17
5-4 Effect of solvent
19
5-5 The frontier Molecular orbital analysis
21
5-6 TDDFT
22
5-7 Topological study of electron density: QTAIM analysis
24
6- Conclusion
28
7- References
30
8- Supporting information
35Côte titre : MACH/0041 Exemplaires (1)
Code-barres Cote Support Localisation Section Disponibilité MACH/0041 MACH/0041 Mémoire Bibliothéque des sciences Français Disponible
Disponible
Titre : Synthesis and Computational Study of New 1H-pyrrol-2-carboxaldehyde [(1E)-(2-hydroxy naphtyl) methylene]hydrazone Type de document : texte imprimé Auteurs : Boucherabine, djihed ; Douniazed HANNACHI, Directeur de thèse Editeur : Setif:UFA Année de publication : 2017 Importance : 1vol. (66f.) Format : 30cm. Catégories : Thèses & Mémoires:Chimie Mots-clés : syntesis,computational,1H-PYRROL-2CARBOXLDEHYDE,methylene,hydrazone Résumé : Conclusion
Quantum chemical calculation results presented above address several
key issues in understanding the structure, IR vibration, UV-vis spectra,
nonlinear optical response, reactivity and protonation mechanism of
the new Azine compounds. On the basis of our studies the following
conclusion can be drawn
-The optimized geometrie of 1H-pyrrol-2-carboxaldehyde [(1E)-(2-hydroxy
naphtyl) methylene]hydrazone with M05-2X functional is in good agreement with the
experimental values
-Comparing the simulated spectra with experimental one, we can notice that
pure B3LYP functional can better reproduce the IR and UV–vis spectra than the
PBEEBE, CAM-B3YP and M05-2X, but empirical dispersion corrections B3LYP-D3
and B3LYP-BJ has better performance than B3LYP.
-The dispersion interactions are largest for Azine-TS and smallest for Azine and
Azine-P. These results reveal that the strengths of dispersion interactions are sensitive
to interaction between H...O and H...N fragments.
-The DFT-D3 dispersion corrections to the thermodynamic energies and kinetic
energies are smaller than the corresponding DFT-BJ dispersion corrections.
- On the other hand and for the first time, our results demonstrate that:
That the polarizabilities and hyperpolarizabilities in solvent phase increase with
the raising of the dipole moment () of the solvated organic compounds and a
large correlation between the (β0 and μ) is obtained.
There is no clear correlation between the dielectric constant of a solvent and its
dipolar moment and the first hyperpolarizability of the title compounds.
Q
58
The rate constants on the protonation process of Azine in solvent phase have a
proportional relation with the dielectric constant of the solvent. On the other
hand, in the backward protonation process the rate constant decrease with the
increasing of the dielectric constant of the solvent.
Our theoretical results demonstrated that, the deprotonation of hydrogen atom
(H2) from the strong cage (H2-O10-C3-C18-C19 and N21) is necessary
condition for the complexation the Azine with metal ion.
We conclude that the title compounds is an attractive object for future studies of
nonlinear optical properties.Note de contenu : Contents
Acknowledgements
iii
List of figures
iv
List of tables
vi
General introduction
1
Reference
2
Chapter 1: Density Functional Theory
I.1.1.The introduction of DFT into chemistry
3
I.1.2.The DFT work in the coordination chemistry lab
4
I.1.2.1.Capabilities of DFT
4
I.2.Basics of the theory of DFT
4
I.3.DFT tools available (Exchange Correlation Functionals)
5
I.3.1. Local density approximation:
7
I.3.2.Generalized-gradient approximation (GGA) :
7
I.3.3.Meta-GGA DFs :
8
I.3.4.Hybrid DFs :
9
I.3.5.Double hybrid DFs
10
I.4.General comments on the most popular density functionals
11
I.5.Jacob’s ladder
12
I.6.Conclusion
14
Reference
15
Chapter 2: results and discussions
II.1. Introduction
17
II.2. Computational method
18
II.2.1. Van der Waals correction
13
II.3. Experimental study
13
II.3.1. The principle
19
II.3.2. General procedure for preparation of Azine
20
II.3.3. The mechanism
21
II.3.4. Spectroscopy
22
II.3.5. Crystal structure determination
24
II.4. Computational study
24
II.4.1. Molecular structures
25
II.4.2. Vibrational modes
26
II.4.2.1. Error analysis of different vibrational calculations
27
II.4.3. Reactivity
28
II.4.3.1. Fukui indices for protonation site identification
29
II.4.3.2. Global reactivity indices
31
II.4.3.3. Local reactivity indices
31
II.4.4. Tautomerization reaction
32
II.4.4.1. H-bond geometries
32
II.4.4.2. Energy barriers and the reaction energies
36
II.4.4.3. The effect of empirical dispersion corrections
37
II.4.5. Nonlinear optical properties
38
ii
II.4.5.1. Polarizability and first hyperpolarizability
40
II.4.5.2. Effect of solvent
45
II.4.5.3. The effect of empirical dispersion corrections
46
II.4.6. TD-DFT
51
II.4.7. Molecular electrostatic potential
53
References
54
conclusion
57
Supplementary-data
59Côte titre : MACH/0048 En ligne : https://drive.google.com/file/d/1MvzzlJ6ec7_qcODQ3gdxypWLWfRhU3tR/view?usp=shari [...] Format de la ressource électronique : Synthesis and Computational Study of New 1H-pyrrol-2-carboxaldehyde [(1E)-(2-hydroxy naphtyl) methylene]hydrazone [texte imprimé] / Boucherabine, djihed ; Douniazed HANNACHI, Directeur de thèse . - [S.l.] : Setif:UFA, 2017 . - 1vol. (66f.) ; 30cm.
Catégories : Thèses & Mémoires:Chimie Mots-clés : syntesis,computational,1H-PYRROL-2CARBOXLDEHYDE,methylene,hydrazone Résumé : Conclusion
Quantum chemical calculation results presented above address several
key issues in understanding the structure, IR vibration, UV-vis spectra,
nonlinear optical response, reactivity and protonation mechanism of
the new Azine compounds. On the basis of our studies the following
conclusion can be drawn
-The optimized geometrie of 1H-pyrrol-2-carboxaldehyde [(1E)-(2-hydroxy
naphtyl) methylene]hydrazone with M05-2X functional is in good agreement with the
experimental values
-Comparing the simulated spectra with experimental one, we can notice that
pure B3LYP functional can better reproduce the IR and UV–vis spectra than the
PBEEBE, CAM-B3YP and M05-2X, but empirical dispersion corrections B3LYP-D3
and B3LYP-BJ has better performance than B3LYP.
-The dispersion interactions are largest for Azine-TS and smallest for Azine and
Azine-P. These results reveal that the strengths of dispersion interactions are sensitive
to interaction between H...O and H...N fragments.
-The DFT-D3 dispersion corrections to the thermodynamic energies and kinetic
energies are smaller than the corresponding DFT-BJ dispersion corrections.
- On the other hand and for the first time, our results demonstrate that:
That the polarizabilities and hyperpolarizabilities in solvent phase increase with
the raising of the dipole moment () of the solvated organic compounds and a
large correlation between the (β0 and μ) is obtained.
There is no clear correlation between the dielectric constant of a solvent and its
dipolar moment and the first hyperpolarizability of the title compounds.
Q
58
The rate constants on the protonation process of Azine in solvent phase have a
proportional relation with the dielectric constant of the solvent. On the other
hand, in the backward protonation process the rate constant decrease with the
increasing of the dielectric constant of the solvent.
Our theoretical results demonstrated that, the deprotonation of hydrogen atom
(H2) from the strong cage (H2-O10-C3-C18-C19 and N21) is necessary
condition for the complexation the Azine with metal ion.
We conclude that the title compounds is an attractive object for future studies of
nonlinear optical properties.Note de contenu : Contents
Acknowledgements
iii
List of figures
iv
List of tables
vi
General introduction
1
Reference
2
Chapter 1: Density Functional Theory
I.1.1.The introduction of DFT into chemistry
3
I.1.2.The DFT work in the coordination chemistry lab
4
I.1.2.1.Capabilities of DFT
4
I.2.Basics of the theory of DFT
4
I.3.DFT tools available (Exchange Correlation Functionals)
5
I.3.1. Local density approximation:
7
I.3.2.Generalized-gradient approximation (GGA) :
7
I.3.3.Meta-GGA DFs :
8
I.3.4.Hybrid DFs :
9
I.3.5.Double hybrid DFs
10
I.4.General comments on the most popular density functionals
11
I.5.Jacob’s ladder
12
I.6.Conclusion
14
Reference
15
Chapter 2: results and discussions
II.1. Introduction
17
II.2. Computational method
18
II.2.1. Van der Waals correction
13
II.3. Experimental study
13
II.3.1. The principle
19
II.3.2. General procedure for preparation of Azine
20
II.3.3. The mechanism
21
II.3.4. Spectroscopy
22
II.3.5. Crystal structure determination
24
II.4. Computational study
24
II.4.1. Molecular structures
25
II.4.2. Vibrational modes
26
II.4.2.1. Error analysis of different vibrational calculations
27
II.4.3. Reactivity
28
II.4.3.1. Fukui indices for protonation site identification
29
II.4.3.2. Global reactivity indices
31
II.4.3.3. Local reactivity indices
31
II.4.4. Tautomerization reaction
32
II.4.4.1. H-bond geometries
32
II.4.4.2. Energy barriers and the reaction energies
36
II.4.4.3. The effect of empirical dispersion corrections
37
II.4.5. Nonlinear optical properties
38
ii
II.4.5.1. Polarizability and first hyperpolarizability
40
II.4.5.2. Effect of solvent
45
II.4.5.3. The effect of empirical dispersion corrections
46
II.4.6. TD-DFT
51
II.4.7. Molecular electrostatic potential
53
References
54
conclusion
57
Supplementary-data
59Côte titre : MACH/0048 En ligne : https://drive.google.com/file/d/1MvzzlJ6ec7_qcODQ3gdxypWLWfRhU3tR/view?usp=shari [...] Format de la ressource électronique : Exemplaires (1)
Code-barres Cote Support Localisation Section Disponibilité MACH/0048 MACH/0048 Mémoire Bibliothéque des sciences Français Disponible
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