Synthesis, characterization and evaluation of new anti-inflammatory iron charge transfer complexes.

The novelty and the essential purpose of this research is the preparation of new anti-inflammatory iron complexes in water green solvent using critical micelle concentration of anionic surface active agent (SAA). Three new anti-inflammatory iron complexes have been prepared. Thiophene-electron (es) donor (D) Schiff base (2-(2-OH-benzylidene)-amino)-4, 5, 6, 7-tetrah ydrobenzo[b] thiophene-3-carbonitrile) has been prepared. Molecular structures of all samples were confirmed based on CNH analysis, 1H NMR and 13C NMR spectra. The molecular structure of Schiff base is further confirmed by computational chemistry using the DFT-B3LYP method, 6-31G (d) basis set. Observed and simulated 1H NMR, UV-Vis. IR/Raman spectra confirmed the molecular structure of D. This Schiff base is intercalated to ferric chloride (FeCl3) giving pure iron charge transfer complex (CTCs). In vitro and kinetic studies confirmed Fe-CTC complexes had (concentration-dependent) potent antimicrobial-, good anti-inflammatory activities. Free radical scavenging activity nitrous oxide (NO.) of Fe (III)CTCs is attributed to geometry Fe(III) ions as distorted octahedral (either monoclinic or triclinic single crystals) via functional groups (-C]N-O, NH2). Elemental analysis and EDS spectra confirmed strong binding between iron and hetero atoms (N, S, O) of D molecules.

Tenability on schiff base Hydrazone derivatives and Frontier molecular orbital.

Context hydrazine compounds based on 1,3,5-triazine were synthesised and their molecular structures were characterised by elemental analysis, Electronic, IR and 1H NMR spectra. The spectral behaviour of the newly prepared compounds in organic solvents of different polarities was extensively studied and correlated to the molecular structure. In this study, 1,3,5-Triazine derivatives (L1, L6, L7, L8) have been subjected to theoretical studies using the Semi-empirical PM3 quantum chemical method. The physical-chemical properties of some Hydrazone derivatives are determined theoretically. The molecular geometry, the Highest Occupied Molecular Orbital (HOMO) - Lowest Unoccupied Molecular Orbital (LUMO) energy gap, molecular hardness (η), ionisation energy (IE), Electron affinity and total energy were analysed, and applications as biological effects were done.

The role of natural biological macromolecules: Deoxyribonucleic and ribonucleic acids in the formulation of new stable charge transfer complexes of thiophene Schiff bases for various life applications.

The ecofriendly cellulose and gelatin provided sustainable and abundant sugars: d-ribofuranose, and 2-Deoxy-ribofuranose (starting reactants for preparative synthetic green chemistry pathways of charge transfer complexes. The natural available sugars d-ribofuranose, and 2-Deoxy-ribofuranose were obtained from facile hydrolysis of cellulose and gelatin natural macromolecules. Successive, low cost and facile alkaline- and acid hydrolysis of Deoxyribonucleic acid (DNA, from gelatin animal source) and ribonucleic acid (RNA, from cellulose plant source) yield the simple sugars: d-ribofuranose and 2-Deoxy-ribofuranose. Eight optically and biologically active charge transfer complexes were prepared from the reaction of the above sugars efficiently intercalated with two new prepared thiophene Schiff Lewis (electron donors) bases: 2-((2Hydroxybenzylidene) amino)-4, 5, 6, 7-tetrahydrobenzo [b] thiophene-3-carbonitrile (D1, 2-((Furan-2ylmethylene) amino) 4,5,6,7 tetrahydrobenzo [b] thiophene-3-carbonitrile (D2). The chemical structures of these prepared Schiff bases were confirmed using the mass spectra. The successful intercalation of the sugar units with the Lewis bases was ascertained using powder x ray diffraction. The molecular structures of the reaction products were proposed based on FTIR, 1H NMR. The optical activity of charge transfer complexes were confirmed using UV-Vis. Absorption spectroscopy. The surface morphology, microstructures, and particle size of the donors and charge transfer complexes were determined using scanning electron microscopy (SEM). The Lewis bases (D1) and (D2) showed no antimicrobial activity, while their charge transfer complexes showed good antimicrobial activity, suggesting their pharmaceutical and medicinal applications due to the potent biological activity against wide spread microbial microorganisms of Gram positive and Gram positive bacteria as well as some fungal species.

Anion induced azo-hydrazone tautomerism for the selective colorimetric sensing of fluoride ion.

The design, synthesis, characterization and their anion sensing properties of two receptors capable of exhibiting azo-hydrazone tautomerism are reported. The anion sensing properties have been investigated using electronic, fluorescence and nuclear magnetic spectral studies in addition to electrochemical and visual detection experiments. Both the receptors selectively bind fluoride ion with >100 nm red-shift in the electronic spectrum and the color changes from yellow to red. The results of the spectral studies revealed that the sensing mechanism involves fluoride ion induced change of chromophore from C=N (hydrazone form) to N=N (azo form) in these receptors leading to the visible color change. Density Functional Theory calculations were conducted to rationalize the optical response of the receptors.

Computational studies of molecular charge transfer complexes of heterocyclic 4-methylepyridine-2-azomethine-p-benzene derivatives with picric acid and m-dinitrobenzene.

Charge transfer complexes of substituted aryl Schiff bases as donors with picric acid and m-dinitrobenzene as acceptors were investigated by using computational analysis calculated by Configuration Interaction Singles Hartree-Fock (CIS-HF) at standard 6-31G∗ basis set and Time-Dependent Density-Functional Theory (TD-DFT) levels of theory at standard 6-31G∗∗ basis set, infrared spectra, visible and nuclear magnetic resonance spectra are investigated. The optimized geometries and vibrational frequencies were evaluated. The energy and oscillator strength were calculated by Configuration Interaction Singles Hartree-Fock method (CIS-HF) and the Time-Dependent Density-Functional Theory (TD-DFT) results. Electronic properties, such as HOMO and LUMO energies and band gaps of CTCs set, were studied by the Time-Dependent density functional theory with Becke-Lee-Young-Parr (B3LYP) composite exchange correlation functional and by Configuration Interaction Singles Hartree-Fock method (CIS-HF). The ionization potential Ip and electron affinity EA were calculated by PM3, HF and DFT methods. The columbic force was calculated theoretically by using (CIS-HF and TD-DFT) methods. This study confirms that the theoretical calculation of vibrational frequencies for (aryl Schiff bases--(m-dinitrobenzene and picric acid)) complexes are quite useful for the vibrational assignment and for predicting new vibrational frequencies.

Molecular complexes of l-phenylalanine with substituted 1,4-benzoquinones in aqueous medium: spectral and theoretical investigations.

Various spectral techniques such as UV-Vis, FT-IR, and fluorescence have been employed to investigate the charge transfer interaction of L-phenylalanine (LPA) with substituted 1,4-benzoquinones (MQ(1-4)). Kinetic and thermodynamic properties of the complexes were determined in aqueous medium at physiological condition (pH=7). The interaction of MQ(1-4) with L-phenylalanine (LPA) was found to proceed through the formation of donor-acceptor complex, yielding a radical anion. The stoichiometry of the complexes was determined by Jobs continuous variation method and was found to be 1:1 in all the cases. Fluorescence quenching studies showed that the interaction between the donor and the acceptors is spontaneous. The results indicated that the progressive replacement of chlorine atom (-I effect) by methoxy group (+M effect) in the quinone decreased the electron acceptor property of the quinone. The order of the experimentally measured association constant of these complexes was well supported by DFT/B3LYP calculations.

Starch-directed green synthesis, characterization and morphology of silver nanoparticles.

Silver nanoparticles were prepared by a simple chemical reduction method using ascorbic acid and starch as reducing and stabilizing agents, respectively. The effect of starch, silver ions and ascorbic acid was studied on the morphology of the silver nano-particles using UV-visible spectrophotometry. The initial reaction time min and amount of starch were important parameters for the growth of Ag-nanoparticles. The morphology was evaluated from transmission electron microscopy (TEM). The truncated triangle nano-plates (from 17 to 30 nm), polyhedron, spherical with some irregular shaped Ag-nanoparticles were formed in presence of starch. Particles are aggregated in an irregular manner, leads to the formation of butterfly-like structures of silver. Starch acts as a stabilizing, shape-directing and capping agent during the growth processes. Silver nanoparticles adsorbed electrostatically on the outer OH groups of amylose left-handed helical conformation in solution.

Spectroscopic studies on the interaction of cilostazole with iodine and 2,3-dichloro-5,6-dicyanobenzoquinone.

The electron accepting properties of the 2,3-dichloro-5,6-dicyanobenzoquinone and iodine and electron donating properties of the drug cilostazole have been studied using the UV-vis, FT-IR, GC-MS and Far-IR techniques. The interaction of cilostazole drug with iodine and 2,3-dichloro-5,6-dicyanobenzoquinone resulted via the initial formation of charge-transfer complex as an intermediate. The rate of formation of the product have been measured and discussed as a function of solvent and temperature. The complexes have been found by Job's method of continuous variation revealed that the stoichiometry of the complexes in both the cases was 1:1. The enthalpies and entropies of formation of the complexes have been obtained by determining their rate constant at three different temperature. The ionization potential of the donor was determined using the charge-transfer absorption bands of the complexes and the same was found comparable with that computed using MOPAC PM3 method.

Studies on the kinetics of growth of silver nanoparticles in different surfactant solutions.

Silver nanoparticles were prepared in aqueous silver nitrate solution using hydrazine as reducing agents in presence of two ionic surfactants (cetyltrimethylammonium bromide; CTAB and sodium dodecyl sulfate; SDS) and one non-ionic surfactant (Triton X-100). The reaction rate was determined spectrophotometrically. The nature of the head group of these surfactants is responsible for the formation of stable, yellow and transparent silver sol. For a certain reaction time, i.e., 20 min, the absorbance of reaction mixture first increased until it reached a maximum, then decreased with [hydrazine]. The reaction follows first-order kinetics with respect to each in [hydrazine] and [Ag(+)]. The results suggest formation of a complex between silver(I) and hydrazine, decomposes in a rate-determining step, leading in the formation of a free radical, which again reacts with the silver(I) in a subsequent fast step to yield the products. The transmission electron microscopic (TEM) images show that CTAB stabilized silver nanoparticles are spherical and of uniform particle size, and the average particle size is about 15 nm.

Charge-transfer complexes of phenylephrine with nitrobenzene derivatives.

The molecular charge-transfer complexes of phenylephrine with picric acid and m-dinitrobenzene have been studied and investigated by IR, 1H NMR electronic spectra in organic solvents and buffer solutions, respectively. Simple and selective methods are proposed for the determination of phenylephrine hydrochloride in bulk form and in tablets. The two methods are based on the formation of charge-transfer complexes between drug base as a n-donor (D) and picric acid, m-dinitrobenzene as pi-acceptor (A). The products exhibit absorption maxima at 497 and 560 nm in acetonitrile for picric acid and m-dinitrobenzene, respectively. The coloured product exhibits an absorption maximum at 650 nm in dioxane. The sensitive kinetic methods for the determination phynylephrine hydrochloride are described. The method is based upon a kinetic investigation of the oxidation reaction of the drug with alkaline potassium permanganate at room temperature for a fixed time at 20 min.

Charge transfer complexes of some oxazolones with iodine.

Molecular charge-transfer (CT) complexes of some oxazolone derivatives with sigma-electron acceptor iodine have been investigated spectrophotometrically in CH2Cl2 at 20 degrees C. Stability constants of the CT complexes formed were computed and discussed in terms of the donor molecular structure and solvent polarity. The thermodynamic parameters of complex formation were determined and discussed. The solid CT complexes have been synthesized and characterized. It was deduced that the complexes formed are of strong n-sigma kind.