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العنوان
Ligational and biological studies on some metal complexes of big molecular and polydentate hydrazones /
المؤلف
Abd El-Hammed, Yasir Khudhur.
هيئة الاعداد
باحث / ياسر خضر عبدالحميد
مشرف / جابر محمد إبراهيم أبوالريش
مشرف / هانى مصطفى مصطفى يوسف
مناقش / صديق عطية صديق
مناقش / مصطفى ابراهيم مصطفى
الموضوع
Hydrazones. Inorganic Chemistry.
تاريخ النشر
2016.
عدد الصفحات
161 p. :
اللغة
الإنجليزية
الدرجة
ماجستير
التخصص
Chemistry (miscellaneous)
تاريخ الإجازة
01/01/2016
مكان الإجازة
جامعة المنصورة - كلية العلوم - Department of Chemistry
الفهرس
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Abstract

The hydrazones and their transition metal complexes have been well documented in the literature as good antimicrobial, anticonvulsant, anticancer, antibacterial and antitumor agents as well as antiviral. The current interest in hydrazones is due to the presence of various donor atoms (N, O-donors), which exhibit diverse bonding modes leading to different structural motifs. The main aim of the present thesis is focused on the preparation and characterization employing elemental analyses, thermal (TG and DrTG), spectral (IR, UV-Visible, 1H and 13CNMR) and magnetic measurements of new complexes of N’1-((E)-2-hydroxy-3H-indol-3- ylidene)-N’3-((E)-2-oxoindolin-3-ylidene) malonohydrazide (H4MDI) and N’1-((E)-2- hydroxy-3H-indol-3-ylidene)-N’3-((E)-2-oxoindolin-3-ylidene) malonohydrazide (H4MDI) with Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Cd(II), Zn(II) and U(VI)O2 metal ions. Some theoretical calculations were carried out using DFT method. The ion-flotation-separation procedure of Cu(II) ions. The biological activity was done. This thesis consists of three Chapters. Chapter 1 displayes different publications concerning the complexation of hydrazones. with a great attention to the compounds similar to that investigated and their biological activities. Chapter 2. covers the experimental part and illustrates the experiments used in this work. It includes a list of reagents, stock solutions along with the physical measurements and instrumentation. The working procedures of computational studies were also discussed as well as a description for the preparation of the ligand and its metal complexes. In addition, this chapter includes the recommended procedures for the antibacterial, antioxidant and the antitumor activity of the prepared metal complexes. Chapter 3. deals with the results and discussion which are summarized to give the following information: 1- The proposed chemical formulae of the ligands and their metal complexes are in good agreement with the stoichiometries concluded from their analytical data of carbon, hydrogen, nitrogen, chloride and metal contents. 2- All complexes have high melting points (>300˚C) and insoluble in most organic Solvents 3- The coordination sites of the ligand, the nature of metal-ligand bonds and the nature of the acetate groups and the existence of the solvated molecules have been elucidated using IR spectra. Different modes of chelation for the investigated ligands are suggested based on careful comparison between the spectra of the ligands and their corresponding complexes. The data obtained are summarized as: •H4MDO As a particle neutral tetradentate in the mononuclear complexes Zn, Cd and U(IV)O2 complexes also as a particle binegative tetradentate in complexes of cobalt and copper. In the complexes of Mn(II) and Ni(II), the H4MHO acts as binegative hexadentate via the enolized (C-OH) with deprotonation, (C=N)azomethine and (C=N)oxime groups. Also H4MDO acts as tetra-negative hexadentate towards Cr(III) and Fe(III) complexes. •In the binuclear Fe(III), Co(II) and Zn(II) complexes, the H4MAI behaves as binegative tetradentate. Also, the H4MAI acts as binegtive hexadentate via the (C=O)isatin, (C=N)azomethine and the enolized (C-O)hydrazide with deprotonation in Cr(III) complex. But in Cd(II) complex the ligand coordinates via the (C=O)hydrazide, (C=N)azomethine and the enolized (C-O)isatin with deprotonation. In addition H4MAI acts as tetranegative hexadentate in the binuclear Ni(II) and UO2 2+ complexes. Moreover, the ligand behaves as trinegative tetradentate in the binuclear Mn(II) Complex 4- The bond angles are quite near to an octahedral geometry predicting d2sp3 or sp3d2 hybridization in complexes of Cr(III), Mn(II), Ni(II) and U(IV)O2+ of both ligands as well as in Fe(III), Zn(II) and Cd(II) complexes of H4MDO. On the other hand, Co(II) and Cu(II) complexes of H4MDO in addition of Fe(III), Co(II) Zn(II) and Cd(II) complexes of H4MDI afforded a tetrahedral geometry with sp3 hybridization. 5- Detailed thermal analysis for the prepared complexes was performed in the temperature range 30-700 or 800˚C. The thermograms show the decomposition steps after which a constant weight is observed corresponding to the remaining part of the complex. 6- In order to assess the influence of the structural properties of the ligands and the type of the metal on thermal behaviour of the complexes, the order (n) and the heat of activation (Ea) of the various decomposition stages are determined from the TG and DrTG using the coats-Redfern and Horowitz-Metzger methods. This section includes also the determination of the thermodynamic parameters of activation (ΔH*, ΔS* and ΔG*) which can be calculated by Erying equation. 7- Ion flotation: Flotation is considered as important treatment technology for this problem and several novel sorbents and processes continuously appear in the scientific literature. Accordingly, the different factors controlling the separation of Ni2+, Pb2+, Cd2+ and Cu2+ ions from different aqueous media were studied. Flotation technique was the best among the well known separation methods because of its simplicity, saving time, accuracy alongside their inexpensive chemicals and equipment. Moreover, this investigation aims to establish the use of oxime hydrazone derivative as good chelating agent and oleic acid as a surfactant in a process known as ion-flotation.The main parameters (i.e. initial solution pH, ligand, surfactant and initial metal ion concentrations, presence of foreign ions and temperature) influence the flotation processes were examined. Moreover, the data showed that about 100% of the metal ions were removed by ion-flotation process at pH 7 and room temperature (25±2oC). The flotation procedure was successfully applied to recover Ni2+, Pb2+, Cd2+ and Cu2+, spiked to some natural water samples, quantitatively under the recommended conditions. This study presents and clarifies the role of flotation for the removal of the toxic metal ions of Ni2+, Pb2+, Cd2+ and Cu2+ from aqueous solutions using oxime hydrazone derivative as good chelating agent with an efficiency of about 100%. Finally, the flotation procedure was succeeded in the recovery of the analytes under investigation from some natural water samples. 8- Antimicrobial and Antimycotic Activities in terms of MIC data of H4MDO, H4MDI and their metal complexes are represented. The compounds were screened for their cytotoxicity assay.