الفهرس | Only 14 pages are availabe for public view |
Abstract The thesis consists of five chapters: introduction, experimental parrt, thermodynamics results, quantum results and biological studies besides Arabic and English summary. Chapter one is general introduction to nano science, nano technology, properties of nano materials, synthesis of nano materials, application of nano materials, properties of used materials in the thesis, solvation, solubility, factors affecting solubility, conductivity, factors affecting conductivity, volumes - densities measurements and cyclic voltametry. Also, this chapter contains some literature survey of published paper in the area of the thesis. Chapter two is experimental part. This chapter contains the materials used, ligands, solvents and their properties, instruments used for measurements such as X-ray diffraction (Xrd), transmittion electron microscopy (TEM), infra-red spectra photometer (FTIR), and preparation of nano-copper sulphate and nano-cadmium chloride. Also, the preparation of saturated solutions of the materials used. Chapter three is about the results and discussion of thermodynamic calculations for nano-copper sulphate, bulk copper sulphate, nano-cadmium chloride and bulk-cadmium chloride in mixed ethanol– H2O solvents ( 10, 20 and 30 % ) by volume at four temperatures (298.15, 303.15, 308.15 and 313.15K ). The solubility of nano-copper sulphate, bulk copper sulphate, nano-cadmium chloride and bulk-cadmium chloride in mixed ethanol – H2O solvents almost decease with increase the mole fraction of ethanol in the mixture while the solubilities of nano-copper sulphate, bulk copper sulphate, nano-cadmium chloride and bulk-cadmium chloride increased by increasing the temperatures. The molar volume (Vm) and Van der Waals (VW) for nano-CuSO4 and bulk-CuSO4 are increased by increasing mole fraction of ethanol in the mixed CH3CH2OH – H2O solvents while the electrostriction volume (Ve) is decreased by increasing mole fraction of ethanol. All types of volume of bulk-CuSO4 are decreased by increasing the temperature. The values of all types of volume of bulk-CuSO4 are higher than that of nano-CuSO4 at all temperatures. The molar volume (Vm) and Van der Waals (VW) for bulk-CdCl2 are decreased by increasing the temperature while the electrostriction volume (Ve) is increased by increasing the temperature. The values of all types of volume of bulk-CdCl2 are higher than that of nano-CdCl2 at all temperatures and mole fractions used. The association parameters (KA and GA) of nano-copper sulphate, bulk copper sulphate, nano-cadmium chloride and bulk-cadmium chloride increase in negativity when the mole fraction of ethanol increase in the solvents mixture while the free energies decrease in negativity when the temperature increase so, the reaction is favourable at low temperature and high value of mole fraction of organic solvent. The association thermodynamic parameters KA and ΔGA for interaction of nano-CuSO4 and bulk-CuSO4 with 1,4-dioxane more than 18- crown-6 more than 12-crown-4 at all temperatures in mixed ethanol-water solvents while the association thermodynamic parameters KA and ΔGA for interaction of nano-CdCl2 with 18-crown-6 more than 12-crown-4 and 1,4- dioxane at all temperatures in mixed ethanol-water solvents. Negative free energies indicate the spontaneous character for all these processes. The complex formation parameters for forming 1:1 and 1:2 stoichiometry complexes were founded from the relation between molar conductance and the ratio of metal to ligand concentration and estimated from conductance titration measurements between the salt and the ligand. The formation of 1:2 and 1:1 stoichiometry complexes are detected from the relation between the molar conductance and [M]/[L] ratio. Two types of stoichiometry complexes are formed in the interaction of nano-copper sulphate, bulk copper sulphate, nano-cadmium chloride and bulk-cadmium chloride with 12-crown-4, 18-crown-6 and 1,4-dioxane in mixed ethanol – water solvents at all temperatures 298.15, 303.15, 308.15 and 313.15K. The complex formation parameters, Kf and ΔGf for forming 1:1 stoichiometry complexes are greater than those forming 1:2 complexes because both the limiting and molar conductances decrease in forming the 1:1 complexes. This means that 1:1 complex is more stable than 1:2 complex for all materials. Cyclic voltammetry measurements using glassy carbon electrode as a working electrode, Ag/AgCl electrode in saturated solution of KCl as a reference electrode and platinum electrode as an auxiliary electrode is take places for the used salts, nano and bulk copper sulphate, nano and bulk cadmium chloride in KCl solution in absence and presence of ligands, 12- crown-4, 18-crown-6 and 1,4-dioxne. Oxidation reduction processes of salts were studied and indicated the mechanism of reactions. Also, the effect of scan rates on the reaction is studied. Cyclic voltammetry measurements take place at two temperatures, 287.15 and 292.15K. The stability constants of complexation, Gibbs free energies, enthalpies and entropies of complexation were estimated and it was found that the nano salts give higher values than bulk salts showing more complexation. The values of interaction of nano copper sulphate with ligands have the following trend: ΔGC (12-crown-4 + nano-CuSO4) > ΔGC (18-crown-6 + nano-CuSO4) > ΔGC (1,4-dioxane + nano-CuSO4) And in case of bulk copper sulphate the trend was: ΔGC (12-crown-4 + nano-CuSO4) > ΔGC (18-crown-6 + nano-CuSO4) > ΔGC (1,4-dioxane + nano-CuSO4) The same trend was found in case of interaction of nano and bulk cadmium chloride with ligands at 287.15 and 292.15K. Chapter four contains theoretical study of the electronic structure, nonlinear optical properties (NLO), and natural bonding orbital (NBO) analysis of 12-crown-4, 18-crown-6 and 1,4-dioxane were investigated using DFT- B3LYP method with 6-311G (d,p) basis set. The optimized structures of the ligands (12-crown-4, 18-crown-6 and 1,4-dioxane) are nonplanar as indicated from the dihedral angles. The HOMO-LUMO energy gap helped in analyzing the chemical reactivity, hardness, softness, chemical potential and electronegativity. Mullikan and natural charge distribution of the molecules, 12-crown-4, 18-crown-6 and 1,4-dioxane were studied which indicated the electronic charge distribution in the molecule 12-crown-4, 18-crown-6 and 1,4-dioxane. The calculated dipole moment and first order hyperpolarizability results indicate that the molecules of 12-crown-4, 18-crown-6 and 1,4-dioxane have a reasonable good linear optical behavior. The NBO analysis indicated the intermolecular charge transfer between the bonding and anti-bonding orbital’s. MEP confirmed the different negative and positive potential sites of the molecule in accordance with the total electron density surface. All the observed bands in the UV spectra can be assigned to (π-π*) transitions as reflected from their intensities. The correspondence between the theoretically computed and the experimentally observed transitions are satisfactory. Chapter five contains study of the biological activity of dibenzo 18- crown-6 as an example of cyclic ether and the biological activity of dibenzo 18-crown-6 with nano and bulk copper sulphate complexes. A comparison between the biological activities of ligand (dibenzo 18-crown-6), nano complex with copper sulphate and bulk complex with copper sulphate indicate that all these compounds are antitumors but the nano complex has a dual effect as an antitumor and antioxidants compound. Also, it is less toxic. |