الفهرس 
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Abstract
Summary and Conclusions
Pyrazolyl quinolinone is an important structural item in several synthetic pharmaceuticals. These Pharmaceuticals are used as antibiotic, anticancer antidepressant, antipsychotic, antiallergic, antihistaminic or anti-inflammatory. The broad activity of this compound attracts the attention of many researchers. Investigation the features of the molecular electronic structure of this compound increases the relevance in understanding its biological activity of molecules.
In the present work some novel pyrazolyl quinolinone derivatives have been investigated. The study includes the investigation of the electronic structure, spectra, nonlinear optical analysis (NLO) and natural bond orbital analysis (NBO) of these compounds.
-The present treatment starts by establishing the most stable structure of pyrazolyl quinolinone derivates keto or enol form, through investigating the ground state geometry and global reactivity descriptors using DFT/B3LYP/6-311++G (d, p) level of theory.
–The electronic and tautomeric structures of some novel pyrazolyl quinolinone derivatives were investigated using DFT/B3LYP/6-311++G (d, p) level of theory. Which showed that the enol Structure (II) is the more stable form than the keto structure (I) in the ground state.
So, the series of our compounds built on enol form.
Compounds R
1 H
2 CH3
3 OCH3
4 Cl
5 NO2
6 Br
The results of computations showed that
-The Egap which measure the chemical reactivity of the studied compounds follows the following order is 1> 3 > 2 >4 > 6 > 5.
-The donating property (oxidation power) which calculated from EHOMO of the studied compounds follows the following order 2 > 3 > 1 > 4 > 6 > 5.
- The accepting property (reducing power) which calculated from ELUMO follows the following order 2 ˂ 3 ˂ 1 ˂ 4 ˂ 6 ˂ 5.
-The results of the MO calculation shows that the computed reactivity in the gas phase of the studied compounds increases in the order: 5 > 6 > 4 > 2 > 3 > 1.
-The order of dipole moment (µ) which indicate the charge distribution of the studied compounds is 3 > 2 > 1 > 6 > 4 > 5.
-The results of the calculated global properties show that the order of decreasing χ(electronegativity) of the studied compounds (1-6) is: 5 > 4 > 6> 1 > 3 > 2.
- The small values of η (chemical hardness) for the studied compounds reflect the ability of charge transfer inside the molecule. Therefore, the order of charge transfer inside the molecule is: 1< 3 < 2< 4< 6 < 5. There is a linear relationship between η and Egap for the studied compounds.
- from the NBO (Natural Bond Orbital) analysis, the most negative centres in the studied compounds 1-6 are O13, O14, O21, N9, N17, N18, N19, N22 atoms, these negative atoms have tendency to donate electrons. Whereas the most electropositive atoms such as C8, C10 have tendency to accept electrons.
-from the NLO (Non-Linear Optical) analysis, the mean first-order hyperpolarizability (β) of the studied compounds 1-6 calculated at the same level of calculation and compared with that of P-nitro aniline (PNA) as a reference (15.5). The order of increasing β parameter is 4 > 3 > 6 > 2 > 5 > 1. The order of the β parameter indicates the promising optical properties of the studied pyrazolyl quinolinone derivatives.
-The molecular electrostatic potential (MEP) shows sites for electrophilic and nucleophilic attack was obtained and confirmed the different negative and positive potential sites of the molecule in accordance with the total electron density surface.
-The Electronic absorption spectra were investigated experimentally in dioxane and ethanol; and theoretically in gas phase, dioxane and ethanol using CAM-B3LYP/6-311 ++G (d, p). -The band maxima (λmax) and intensities of the spectra are solvent dependent.
- The bands of compounds 1, 2, 3, 5 and 6 showed blue shift, while compound 4 shows red shift by increasing solvent polarity on going from dioxane to ethanol.
- Theoretical calculations of the vertical excitations at the CAM-B3LYP/6-311 ++G (d, p) reproduce the experimental spectra, indicating a good agreement between theory and experiment.
-The NBO analysis of the compounds 1, 5 and 6 indicates the intermolecular charge transfer between the bonding and antibonding orbitals.
As a novel industrial application for compound 1 (R=H) and compound 2 (R=CH3) is using it as disperse dyes for dying polyester (PET).
The results showed that
-The dye uptake values by polyester fabrics carried out by using HT (high temperature) dyeing method at 130 oC generally was higher than those obtained by conventional dyeing methods at 100oC.
- Compound 1 as a disperse dye showed better exhaustion and color strength than compound 2 at conventional dyeing method
– Compound 2 dye showed better exhaustion than compound 1at HT dyeing. Compound 1showed a better brightness at low and high temperatures.
-The computation using hyperchem program explains the high uptake of compound 1 due to its small calculated volume.
In the present work we used the various computational method to understand the removal of cationic dyes from wastewater (Which represent a serious damage for humanity and aquatic system) via adsorption technique. The adsorption of single malachite green (MG), maxilon blue (MxB) and their mixture in water in different ratios was simulated theoretically.
ɤ-alumina nanoparticles are used as adsorbent and adsorption process has been simulated theoretically using DFT/B3LYP /6-31G (d,p ) level of theory.
Some experimental parameters, namely, pH, adsorbent dose, reaction temperature, dye solution concentration and contact time, were studied. Different adsorption kinetics and isotherms models were studied.
The experimental thermodynamics studies were done.
The obtained results revealed that
-The optimum conditions for effective adsorption of both MG and MxB were (PH >7, dye conc = 50 ppm, adsorbent dose 0.1g) and (pH=10, dye conc. = 100 ppm, adsorbent dose = 0.05 g), respectively.
-The adsorption of both sole dyes was found to obey pseudo- second- order model and Freundlich isotherm for adsorption kinetics and isotherms models, respectively.
–Thermodynamic parameters were calculated for the adsorption of malachite green dye. The results indicates that the adsorption is a spontaneous, physical and endothermic process.
-The adsorption of mixed cationic dyes (MG and MxB) emphasized the absence of selectivity towards the removal of one of them from the water in a binary system.
-The full geometry optimization of malachite green, maxilon blue and cationic mixture dyes with ratio 1:1 was performed by applying B3LYP/6-31G (d, p) level of theory.
-The results of calculation showed that the Egap of MG cationic form is lower (more active) than the neutral one by 46 kcal mol-1, this explain why the cationic form of MG is adsorbed on Al2O3 surface more strongly than neutral form.
–For the theoretical simulation, two molecules of the cationic MG and one molecule of Al2O3 is used to form MG-Al2O3 complex.
-The results of simulation showed that:
)i (The optimized bond length between MG (N) and the Al-oxide (O) is 1.5 Å (the experimental N-O is 1.360 Å),
)ii( The calculated binding energy (BE) for MG-Al is (698 kJ) (i.e., the BE for one N-O bond is 344 kJ). The experimental BE for N-O is 631 kJ. The BE of the N-O in MG-Al is half of the actual N-O bond which explain a possible physical adsorption. The observed increase in the length from 1.4 Å to 1.5 Å in N-O bond between MG and Al surface indicated the physical adsorption of MG on Al2O3 surface.
-The computed β parameter for neutral MG is 7 times greater than PNA, while the cationic MG is 18 times greater than PNA and the complex MG-Al2O3 is 117 times greater than PNA; implying their promising applications as NLO materials.
-The computational study for maxilon blue MxB showed the optimized bond length N-O between MxB (N) and the Al-oxide (O) is 1.38Å (the experimental N-O is 1.36 Å). The increase in the N-O bond between MxB and Al surface confirmed the physical adsorption of MxB on Al2O3 surface.
-For the binary system of two cationic dyes the studied MG-Al2O3-MxB complex was optimized at the same level of theory.
-The analysis of the β parameter for the studied molecules showed that the MxB is 61 times greater than PNA, the complex MxB-Al2O3 is 125 times greater than PNA, and the complex MG-Al2O3-MxB is 534 times greater than PNA implying their promising applications as NLO materials.
-The variation of Hyper-Rayleigh scattering (βHRS) and the depolarization ratio (DR) can be rationalized by complexation and structural evidence. The high value of βHRS and DR, of the MG and MxB and the lowest value in case of Al2O3 confirms long bond length between N-atom of MxB and of MG with O-atom of Al-oxide and hence weak bonding which resulting in a physisorption process.
- Further, the interaction has been assigned to electrostatic forces between the cationic groups (–N+) of MxB and MG as sole and mixed (equal ratio) and the negatively charged groups (-Al-O-) on alumina surface. Finally, the mechanism of interaction through single and binary system was discussed and supported by computational study.