Sharif Digital Repository

Salicylaldehyde-amino acid Schiff base complexes are used as non-enzymatic models for the metal-pyridoxal (Vitamin B6) amino acid Schiff base systems which are key intermediates in many metabolic reactions of amino acids catalyzed by enzymes which require pyridoxal as a cofactor (transamination, decarboxylation, α and β elimination, racemization, etc.). In addition, complexes of amino acid Schiff bases are considered to constitute new kinds of potential anticancer, antitumor, antiradical and antibacterial reagents. On the other hand nuclear magnetic resonance imaging (MRI), has become a powerful tool for clinical diagnostics thanks to the development of a new class of pharmaceuticals... 

This study involved the synthesis, structural characterization and studies of gadolinium (III) hexaaza macrocyclic Schiff base complexes containing pyridine head and their decomposition in aqueous solution.There are many applications of lanthanide(III) macrocyclic complexes as medicine and in the biological systems, as magnetic resonance imaging (MRI) agents, and etc.These applications require that the Gd(III) complexes be resistant to gadolinium ion release under physiological conditions.
We considered planer macrocyclic ligands as a means to obtain highly stable complexes of Gd(III). Symmetric [2+2] Schiff base macrocyclic derived from 2,6-diacetylpyridine with amines would exhibit... 

Folic acid is a pterin derivative containing a glutamyl moiety and essential for biological reactions. Pterins are a class of heterocyclic compounds with unique structures and biological functions. Tetrahydrobiopterine has been known to be essential for catalytic hydroxylation of aromatic amino acids by metal ions-containing aromatic amino acid hydroxylases. Metal ions at the active site of these enzymes have been inferred to be closely associated with the pterin cofactors in the catalytic reactions.Information on pterin-metal interaction may give clues to the role of metal ions in enzymatic reactions. With these points in mind, studies have been conducted to verify the formation of ternary... 

Ternary copper (II) complexes having heterocyclic bases and α-amino acid salicylaldiminates
as models for the type-2 sites in copper oxidases are of great biological importance. Considerable attention has given to mixed ligand complexes due to their antitumore, antimicrobial , inflammatpry , ascorbate oxidase (AO) and dopamine β-hydroxylase(DβH) and radio- imaging properties. With this in mind, new copper (II) complexes including amino acid Schiff base and heterocyclic bases (1,10 phenanthroline and 2, 2 biprydine ) have been synthesized, investigated and characterized by IR, UV-Vis and CHN. In the case of amino acid Schiff-base complexes, the tridentate ONO Schiff base ligand... 

The optical properties of semiconductor nanoparticles are dependent on their size. Then, the important problem in synthesized semiconductor nanoparticles is controllable of their size. In this research ZnS nanoparticles were synthesized by hydrothermal method and taguchi design of experiments and study on effect of solvent, reaction temperature and molar precursor ratio on band gap and particle size of ZnS . The UV-Vis spectrum was carried out for measurement of band gap and the size of nanoparticles by using the effective mass approximation. The X-ray diffraction patterns exhibited a cubic zinc blende structure for the nanoparticles. The ZnS:Mn +2 nanoparticles werw synthesized. With... 

In the contest of conversion of water to hydrogen and oxygen there is a need for catalysts which will effectively support the oxidation of water. In nature, photosystem II relies on manganese for the oxidation of water. The water oxidizing complex (WOC) contains a cluster of four manganese atoms. In the past few years, there has been a tremendous surge in research on the synthesis of various manganese compounds aimed at simulating WOC of PS II. In this project, several manganese oxides as heterogeneous catalysts in water oxidation have been synthesized and characterized by FT-IR, X-ray diffraction, TGA, XPS, SEM and BET. Some of these oxides are able to oxidize water in the presence of... 

Studying of synthetic models which have many similarities to Oxygen Evolving Complex (OEC) in Photosystem II (PS II) can play a very significant role in gaining an insight to mechanism of oxidation of water in PS II. The aim of this study is to investigate the mechanistic and kinetic aspects of oxidation of dopamine as an important neurotransmitter in body by tri and tetranuclear oxo-bridge manganese clusters which have been reported in the past to get some information about the influence of protonation and deprotonation of oxo-bridges and water molecules bonded to these clusters on properties of them in redox reactions.In aqueous media, the trinuclear complex... 

Self-Assembled Monolayer (SAM) is the first step in all surface engineering and assembly processes. It is used in sensor fabrication, memories and molecular recognition and optoelectronic devises as an active surface for patterning and chemical architecting of solid substrates. Tetraphenyl porphyrins because of their high stability and uniqe electronic and optic properties, that comes from their conjugate π electrons, easily can be used in these monolayers. Moreover they have a wide application because of their ability for coordination with metals and accepting substituents with electron donating and withdrawing properties. Electron transport through these layars which attach to the surface... 

In order to have more understanding of the cooperative effect between the metal centers in the multimetallic complexes, on their physicochemical properties and chemical reactivity, some new bi- and tetra-nuclear Cu(II), Ni(II) and Pd(II) complexes of compartmental binucleating ligands were synthesized and characterized. In this study, a series of new compartmental binucleating thiophenol-based proligands PL1-PL4 from the Schiff base condensation of 2 equiv. of o-aminophenol or 2-amino-4-methylphenol with 1 equiv. of 2,6-diformyl-4-alkyl- thiocarbamoyl were synthesized and characterized. New Bi- and tetra-nuclear copper (II) complexes derived from these binucleating compartmental... 

The complexation between folic acid and the complexes of Cu(L)2 (L = Glycine, Alanine, Valine) were investigated using UV.Vis spectroscopy. The values of the equilibrium constant K and molar absorption coefficient Ɛ of the complexes were estimated in the aquation environment at various temperatures. The temperature dependence of the K can be used for the determination of the thermodynamic reaction quantities (∆G, ∆H, ∆S) for linear regression fits to the Van’t Hoff equation. The kinetic studies reveals that the stoichiometry of reaction were 1:1 for these systems. All reaction were endothermic and the values of the ∆H are positive. In all cases entropy increased and the values of the ∆S... 

Due to study of reactivity and interaction of Schiff base complexes, as models of biological system such as vitamin B (B6 and B12) and enzyme (cytochtome c oxidase), some mono and binuclear Zn(II), Pd(II) and Co(II) Schiff base complexes were synthesized and characterized. As a model for vitamin B6, tridentate Schiff base ligands derived from the condensation of water soluble aldehyde with the amino acids (glycine, L-alanine, L-valine, L-leucine and L-phenylalanine) in the presence of Zn (OAc)2.2H2O give rise to the formation of five new water soluble Zn(II) complexes. The IR spectra of these complexes show that, there are prominent stretching vibration of the azomethine band (HC=N) at... 

The charge transfer interaction of two Schiff-bases Bis- (2-thiophene methylene)-1,4- Benzene Di amine and Bis (2-thiophene methylene)-1,3- Benzene Di amine as donors with iodine and tetracyano ethylene as Electron acceptors have been studied spectrophotometrically. The formation constants and extinction coefficients of charge transfer complexes have been determined by graphical as well as iterative methods. From measurements at different temperatures the thermodynamic functions of the charge transfer complex formation have been studied. The temperature dependence of the K can be used for the determination of the thermodynamic reaction quantities (ΔG˚, ΔS˚, ΔH˚) for linear regression fits... 

Donor-acceptor adducts of selenium dioxide were formed with tree aromatic amines, two aliphatic amines and tree pyridine like bases. Characterization of these adducts were done through UV-Vis Spectrophotometer and IR Spectrophotometer and NMR Spectroscopy. In addition, the stoichiometry of these adducts were identified by elemental analysis (CHN). To approve the existence of selenium, Atomic absorption instrument was used.The results obtained from the entioned methods show that the adduct formation between selenium dioxide with amines and pyridine like bases are in following order: p-phenylen diamine.SeO2>NH5.SeO2,en.SeO2,cyclohexylamine.SeO2,... 

Molecular nanomagnets, also known as Single Molecule Magnets (SMMs) are a class of molecules that at low temperature exhibit magnetic hysteresis of pure molecular origin and not related to a cooperative effect. In the past fifteen years they have attracted great interest for their potentiality to act as magnetic memory units and for the many quantum effects in the dynamics of their magnetization. Organization of SMM on surfaces is the first step in order to address the magnetic state of a single molecule or to connect the molecule to a conducting substrate. The complex nature of SMMs and the peculiar origin of their magnetic bistability have been representing for half a decade an obstacle to... 

In order to obtain more insight into the enzymatic oxygen-atom-transfer (OAT) process and elucidate the relation between the structure and function of the synthetic model complexes, new molybdenum and tungsten complexes containing different chelating ligands were systematically prepared and investigated. Herein, the cis-dioxo-molybdenum(VI) complexes with new aromatic dithiolene ligands, formulated as [MoO2(2,3ppdt)2]NR4 and [MoO2(3,4ppdt)2]NR4, (2,3ppdt= pyrido-2,3-pyrazine-2,3-dithiolato, 3,4ppdt= pyrido-3,4-pyrazine-2,3-dithiol and R= Et or Bu) were prepared and investigated by elemental analysis, IR, 1H NMR and UV-Vis spectroscopic methods. An OAT reaction of [MoO2(2,3ppdt)2]2– with PPh3... 

The aim of this study is to mimic water oxidizing complex to find new materials and also to understand their rules in this matter. To achieve this, manganese complexes containing 2,4,6-tris (2-pyridyl)-1,3,5-Triazine, 1,10-phenanthroline, 1,10-bipyridine, Schiff base, amino acids, 2,6-pyridinedicarboxylic acid, 2-pyridinecarboxylic acid have been synthesized and characterized by elemental analysis, IR, EPR, ESI-MS, electronic absorption spectroscopy, electrochemistry, X-ray diffraction and oxygen evolution in presence of oxone and Ce(IV). It is shown that the reaction between Mn(II) complexes containing 2,4,6-tris¬(2-pyridyl)-1,3,5-Triazine, 1,10-phenanthroline, 1,10-bipyridine,... 

The charge transfer interaction of two Schiff-bases 2,5-dichloro -bis(thiophen-2-ylmethylene)benzene-1,4-diamine and 2,5-dimethyl-bis(thiophen-2- ylmethylene) benzene-1,4-diamine as donors with I2 and TCNE ethylene as acceptors have been studied spectrophotometrically.
The formation constants and extinction coefficients of charge transfer complexes have been determined by graphical as well as iterative methods. From measurements at different temperatures the thermodynamic functions of the charge transfer complex formation have been studied. The temperature dependence of the K can be used for the determination of the thermodynamic reaction quantities (ΔG, ΔS, ΔH) for linear regression... 

In the first part of this thesis, the application of metal oxide nanoparticles in oxidative degradation of methylene blue is discussed. Nanoparticles of manganese tungstate (MnWO4) were prepared via an impregnation method using Mn(NO3)2.4H2O and WO3 as a source of Mn and W, respectively. The morphology of the manganese tungstate nanoparticles was studied in detail by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). MnWO4 nanoparticles showed severe catalytic performance for the degradation of organic dye (methylene blue) in the presence of tertiary-butyl hydrogen peroxide, TBHP, as the oxidant at room temperature in water. Mn doped ZnO... 

In this project some samples from the water which enters the plant and the effluent water were analyzed and the results were compared due to investigating the quality of water in Sangan mine tailing dams. Considering that Northern C mass contains more than two percent sulfur, it can produce AMD. Acid Mine Drainage (AMD), which is caused by the oxidation of sulfide ores in the mines, is the most important environmental problem. Anticipating potential problems of this waste can prevent the problem. To predict it, Acid-Base Accounting (ABA) test was used. The experiment's parameters like Maximum Potential Acidity (MPA) and Neutralization Potential (NP) were measured for more than 130 samples... 

Epoxidation of alkenes by Mn(III)meso-tetra(4-sulfonatophenyl)porphyrin chloride (MnTPPS4Cl) in the various homogeneous and heterogeneous catalytic systems was investigated. In the case of homogeneous catalysis, epoxidation of cyclooctene in CH2Cl2/MeOH mixture using urea hydrogen peroxide (UHP) as an oxidant and imidazole as a co-catalyst results in the formation of cycloocetene oxide in 87% yield. Using this catalytic system various alkenes successfully oxidized to their corresponding epoxide in high conversions and selectivity. Cyclic alkenes oxidized more easily than linear alkenes. In addition, epoxidation of alkenes was investigated in the heterogeneous catalytic systems. For this...