Effect of nanocavity confinement on the rotational relaxation dynamics: 3-acetyl-4-oxo-6,7-dihydro-12H indolo-[2,3-a] quinolizine in micelles

In continuation of our recent study on the steady state photophysics of a biologically active beta-carboline derivative, 3-acetyl-4-oxo-6,7-dihydro-12H indolo-[2,3-a] quinolizine (AODIQ), in the present article we have investigated the effect of nanocavity confinement on the excited state dynamics and rotational relaxation of the probe using picosecond time resolved fluorescence and fluorescence anisotropy techniques. The polarity dependent intramolecular charge transfer process is responsible for the remarkable sensitivity of this biological fluorophore in micellar environments. The fluorescence anisotropy decay of AODIQ incorporated inside the micelle is biexponential. The rotational motion of the probe was interpreted on the basis of a two step model consisting of a fast restricted rotation of the probe and a slow lateral diffusion of the probe in the micelle; both coupled to the overall rotation of the micelle. Experimental results reveal that micellar environment causes significant retardation of both the wobbling as well as the translational motion of the probe.     

Indirect determination of vanadium by atomic absorption spectrometry

An indirect method for the determination of vanadium as vanadate by atomic absorption spectrometry is described. In neutral medium, vanadate forms a stable ion-association complex with copper (II) and biguanide, which is extractable into butanol with an efficiency higher than 99%. The copper content in the extract (and hence indirectly VO^?₃) is determined by aspirating it directly into an acetylene flame. The calibration graph is linear up to 3.4 μg ml^?1 of VO^?₃. The limit of detection is 16 ng ml^?1. Only chromium interferes.     

Effect of cobalt substitution on microstructure and magnetic properties in ZnO nanoparticles

Ferromagentic semiconductors have been actively pursued because of their potential as spin polarized carrier sources and easy integration into semiconductor technology. One such material, ZnO has been shown to be a potential Diluted Magnetic Semiconductor (DMS). The appearance of ferromagnetism, however, is found to be sensitive to the processing conditions. We report synthesis of ZnO nanoparticles of size ∼20 nm by a simple co-precipitation technique using metal nitrates and NaOH as precipitant. The particles are self-organised and reveal single crystalline behaviour in electron diffraction pattern. Incorporation of Co in ZnO matrix leads not only to the reduction in crystallite size but also to the modification of the structure. At 5% Co, the particles are highly textured. The particles also aggregate and the aggregated mass have nearly rectangular shape as seen through TEM. Increasing Co to 10%, results into further reduction of particle size and the particles self organize in a line, which looks like nanofibers. This alignment of particles increases by increasing the Co content further. This type of growth of nanofibers above Co ≥ 10% is well correlated with the anisotropic peak broadening observed in the XRD spectra. In addition, Co substitute Zn site up to 20% without showing any extra phase in XRD spectra as compared to 7 to 10% in case of bulk. Transport and magnetic studies indicate that conductivity increases with increasing Co content, but carrier mediated ferromagnetism is absent down to 10 K.      

Exact diffusion constant of a one-dimensional asymmetric exclusion model with open boundaries

For the 1D fully asymmetric exclusion model with open boundary conditions, we calculate exactly the fluctuations of the current of particles. The method used is an extension of a matrix technique developed recently to describe the equatime steady-state properties for open boundary conditions and the diffusion constant for particles on a ring. We show how the fluctuations of the current are related to non-equal-time correlations. In the thermodynamic limit, our results agree with recent results of Ferrari and Fontes obtained by working directly in the infinite system. We also show that the fluctuations of the current become singular when the system undergoes a phase transition with discontinuities along the first-order transition line.     

Observation of grain growth in swift heavy ion irradiated NiO thin films

NiO thin films grown on Si(100) substrates by electron beam evaporation, were sintered at 500 °C and 700 °C. The films were irradiated with 120 MeV Au⁹⁺ ions. Irradiation had different effects depending upon the initial microstructure of the films. Irradiation of the films at a fluence of 3 × 10¹¹ ions cm⁻² leads to grain growth for the films sintered at 500 °C and grain fragmentation for the films sintered at 700 °C. At still higher fluences of irradiation, grain size in 500 °C sintered film decreased, but the same improved in 700 °C sintered film. Associated with the grain size, texturing of the films was also shown to undergo significant modifications under irradiation.     

Kinetic and mechanistic studies on the reaction of thiosemicarbazide with [(H<Subscript>2</Subscript>O)(tap)<Subscript>2</Subscript>RuORu(tap)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)]<Superscript>2+</Superscript> {tap = 2-(m-tolylazo)pyridine}

The interaction of thiosemicarbazide with the title complex has been studied spectrophotometrically in aqueous medium as a function of [complex], [thiosemicarbazide], pH and temperature at constant ionic strength. At pH 7.4, the reaction shows two distinct paths; both of which are [thiosemicarbazide] dependent. A parallel reaction scheme fits well with the experimental findings. An associative interchange mechanism is proposed for both the paths; the activation parameters calculated from Eyring plots are ΔH₁^≠ = 14.2 ± 0.8 kJ mol⁻¹, ΔS₁^≠ = −241 ± 2 JK⁻¹ mol⁻¹, ΔH₂^≠ = 30.8 ± 1.4 kJ mol⁻¹ and ΔS₂^≠ = −236 ± 4 JK⁻¹ mol⁻¹. From the temperature dependence of the outer sphere association complex equilibrium constants, the thermodynamic parameters calculated are ΔH₁^° = 34.25 ± 1.9 kJ mol⁻¹, ΔS₁^° = 146 ± 6 J K⁻¹ mol⁻¹ and ΔH₂^° = 9.4 ± 1.1 kJ mol⁻¹, ΔS₂^° = 71 ± 3 JK⁻¹ mol⁻¹, which gives a negative ΔG° at all temperatures studied, supporting the spontaneous formation of an outer sphere association complex.     

Structural and magnetic properties of Fe doped NiO

Mott-Hubbard anti-ferromagnetic insulator, NiO shows p-type semiconducting behaviour due to vacancy at Ni²⁺ site in its bunsenite structure. We report the modification of structural and magnetic order in NiO on Fe doping. NiO samples at different Fe concentrations in the range 0 to 5 at.% have been prepared by chemical co-precipitation and post thermal decomposition method. Both structural and magnetic characterization reveal that with increasing Fe doping concentration, NiO evolves as a magnetically inhomogeneous state out of the parent homogeneous antiferromagnetic state. In addition, structural inhomogeneity was also observed with Fe precipitating to γ-Fe₂O₃ phase, the signature of which could be clearly seen for Fe content beyond 2 at.%. At lower Fe content however, some amount of Fe occupies lattice and interstitial sites in the NiO matrix and drive the latter to acquire ferromagnetic ordering, which was evident from a clear hysteresis loop at 300 K.      

Invariant Solutions of Inhomogeneous Universe with Electromagnetic Field in Lyra Geometry

The present study deals with the cylindrically symmetric inhomogeneous cosmological models for perfect fluid distribution with electro-magnetic field in Lyra geometry. Lie group analysis has been used to identify the generators (symmetries) that leave the given system of partial differential equations (field equations) invariant. With the help of canonical variables associated with these generators, the assigned system of partial differential equations is reduced to an ordinary differential equations whose simple solutions provide nontrivial solutions of the original system. They obtained a new class of invariant (similarity) solutions by considering the potentials of metric and displacement field are functions of coordinates t and x. The physical behavior of the derived models are also discussed.     

Fabrication of a nanostructured gold-polymer composite material

A facile synthesis route is described for the preparation of a poly-(o-aminophenol)-gold nanoparticle composite material by polymerization of o-aminophenol (AP) monomer using HAuCl₄ as the oxidant. The synthesis was carried out in a methanol medium so that it could serve a dual solvent role, a solvent for both the AP and the water solution of HAuCl₄. It was found that oxidative polymerization of AP leads to the formation of poly-AP with a diameter of 50±10nm, while the reduction of AuCl₄ ^- results in the formation of gold nanoparticles (∼ 2nm). The gold nanoparticles were uniformly dispersed and highly stabilized throughout the macromolecular chain that formed a uniform metal-polymer composite material. The resultant composite material was characterized by means of different techniques, such as UV-vis, IR and Raman spectroscopy, which offered the information about the chemical structure of polymer, whereas electron microscopy images provided information regarding the morphology of the composite material and the distribution of the metal particles in the composite material.     

Photophysical study of 3-acetyl-4-oxo-6,7-dihydro-12H-indolo[2,3-a]quinolizine in biomimetic reverse micellar nanocavities: a spectroscopic approach

Photophysical properties of 3-acetyl-4-oxo-6,7-dihydro-12H-indolo[2,3-a]quinolizine (AODIQ), a bioactive molecule, has been investigated in well-characterized, monodispersed biomimicking nanocavities formed by sodium bis(2-ethylhexyl)sulfosuccinate (AOT) in heptane using steady-state and picosecond time resolved fluorescence and fluorescence anisotropy. The emission behavior of AODIQ is very much dependent upon the water/surfactant mole ratio (W), i.e., on the water pool size of the reverse micellar core. AODIQ exhibits a sharp decrease in fluorescence anisotropy with increasing W, implying that the overall motional restriction experienced by the molecule is decreased with increased hydration. Some of the depth-dependent relevant fluorescence parameters, namely, fluorescence maxima and fluorescence anisotropy (r), have been monitored for exploiting the distribution and microenvironment around the probe in the reverse micelles. Fluorescence spectral position and fluorescence quenching studies suggest that the probe does not penetrate into the reverse micellar core; rather it binds at the interfacial region. Quantitaive estimates of the micropolarity and microviscosity at the binding sites of the probe molecule have been determined as a function of W.