Role of ligand to control the mechanism of nitric oxide reduction of copper(II) complexes and ligand nitrosation

The nitric oxide reactivity of two copper(II) complexes, 1 and 2 with ligands L(1) and L(2), respectively, [L(1) = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, L(2) = 5,5,7-trimethyl-[1,4]-diazepane] have been studied. The copper(II) center in complex 1 was found to be unreactive toward nitric oxide in pure acetonitrile; however, it displayed reduction in methanol solvent in presence of base. The copper(II) center in 2, in acetonitrile solvent, on exposure to nitric oxide has been found to be reduced to copper(I). The same reduction was observed in methanol, also, in case of complex 2. In case of complex 1, presumably, the attack of nitric oxide on the deprotonated amine is the first step, followed by electron transfer to the copper(II) center to afford the reduction. Alternatively, first NO coordination to the Cu(II) followed by NO(+) migration to the secondary amine is the most probable in case of complex 2. The observation of the transient intermediate in UV-visible and FT-IR spectroscopy prior to reduction in case of complex 2 also supports this possibility. In both cases, the reduction resulted into N-nitrosation; in 1, only mononitrosation was observed whereas complex 2 afforded dinitrosation as major product along with a minor amount of mononitrosation. Thus, it is evident from the present study that the macrocyclic ligands prefer the deprotonation pathway leading to mononitrosation; whereas nonmacrocyclic ones prefer the [Cu(II)-NO] intermediate pathway resulting into nitrosation at all the available sites of the ligand as major product.     

Reduction of copper(II) complexes of tridentate ligands by nitric oxide and fluorescent detection of NO in methanol and water media

Two copper complexes, 1 and 2, with tridentate N-donor ligands, L(1) and L(2) [L(1)= (1-methyl-1H-imidazol-2-ylmethyl)-(2-pyridin-2-yl-ethyl)amine, L(2) = (2-pyridin-2-yl-ethyl)-pyridin-2 yl-methylamine] respectively, have been synthesized and characterized. On exposure to nitric oxide, the copper(II) centers in complexes 1 and 2 were found to undergo reduction in various solvents. In acetonitrile solvent the reduction was accompanied by a simultaneous N-nitrosation on the secondary amine center on the ligand frameworks. Complexes 3 and 4 were prepared with ligands L(3) and L(4), respectively. L(3) and L(4) [L(3) = 5-dimethylamino-naphthalene-1-sulfonic acid (1-methyl-1H-imidazol-2-ylmethyl)-(2-pyridin-2-yl-ethyl)-amide; L(4) = 5-dimethylamino-naphthalene-1-sulfonic acid(2-pyridin-2-yl-ethyl)-pyridin-2-ylmethyl-amide] are the dansyl derivatives of L(1) and L(2), respectively. Complex 4, due to paramagnetic quenching, does not display any fluorescence; however, on addition of nitric oxide to a methanol or water solution of complex 4, the fluorescence intensity of the fluorophore has been found to be restored. This is attributed to the reduction of the Cu(II) center by nitric oxide to diamagnetic Cu(I). The turn-on of quenched fluorescence intensity has been observed both in methanol and water media.     

Synthesis of some tetrazole fused pyrido[2,3-c]coumarin derivatives from a one-pot three-component reaction via intramolecular 1,3-dipolar cycloaddition reaction of azide to nitriles

Some novel tetrazole fused pyrido[2,3-c]coumarin derivatives 5/7/9 were synthesized from a one-pot three-component reaction of 4-chloro-3-formylcoumarins 2, sodium azide 3, and alkyl/aryl acetonitriles 4/6/8.     

Effect on thermoluminescence parameters of biotite mineral due to thermal quenching

The Thermally Stimulated Luminescence (TSL) at room temperature X-ray irradiated natural biotite in form of micro-grain powder was studied under various heating rates. TSL peaks showed at temperatures 393 K, 399.6 K, 403.5 K, 404.5 K, 406.9 K at their respective heating rates 2 K/s, 4 K/s, 6 K/s, 8 K/s and 10 K/s. The effect of thermal quenching on thermoluminescence parameters such as peak maximum temperature, peak area, FWHM, geometrical symmetry factor, the activation energy were investigated. From the symmetry factor it is clear that the TL glow curve follows the first order kinetics for the lowest heating rate, but as the heating rate increases it defers from the first order. The activation energies for each heating rates were calculated by using Chen peak shape methods for general order kinetics and found to be decreased for higher heating rates. When activation energy is calculated by variable heating rate method it is observed that the method overestimated the value of activation energy and pre-exponential frequency factor significantly due to thermal quenching.     

A New Approach to Energy Integral for Investigation of Dust-Ion Acoustic(DIA)Waves in Multi-Component Plasmas with Quantum Effects in Inertia Less Electrons

Dust-ion acoustic waves are investigated in this model of plasma consisting of negatively charged dusts,cold ions and inertia less quantum effected electrons with the help of a typical energy integral.In this case,a new technique is applied formulating a differential equation to establish the energy integral in case of multi-component plasmas which is not possible in general.Dust-ion acoustic(DIA) compressive and rarefactive,supersonic and subsonic solitons of various amplitudes are established.The consideration of smaller order nonlinearity in support of the newly established quantum plasma model is observed to generate small amplitude solitons at the decrease of Mach number.The growths of soliton amplitudes and potential depths are found more sensitive to the density of quantum electrons.The small density ratio r(=1-f) with a little quantized electrons supplemented by the dust charges Z_d and the in-deterministic new quantum parameter C_2 are found responsible to finally support the generation of small amplitude solitons admissible for the model.     

Radiation‐Grafted Polymerization from a Gas Phase to Form Polymeric Layers on Metal Surfaces

Summary: Experimentally it is shown that, under irradiation in an atmosphere of non‐saturated vinylidene chloride vapors, a polymeric layer is formed on the surface of oxidized titanium samples. The thickness of this layer increases with the increase of thickness of the oxide film. Such a dependence corresponds to the current understanding of the mechanism of formation and migration of the active excited centers that initiate grafted polymerization.

Wide range XPS spectra of oxidized titanium samples after PVDC grafting from a gas phase.