Studies on binuclear hydroxo/carboxylato-bridged manganese(III) complexes and a mononuclear manganese(III) complex involving salen type ligands

Synthesis of six hydroxo-bridged binuclear manganese(III) complexes of formulae [MnL-X-MnL](ClO₄) [X = OH (1–6)] along with a mononuclear manganese(III) complex (7) [Mn(L)(L′)(MeOH)₂] [HL′ = 2-(2-hydroxy-phen-yl)benzimidazole] and two carboxylate-bridged binuclear manganese(III) complexes (8) and (9) are described. The complexes have been characterized by the combination of i.r., u.v.-vis spectroscopy, magnetic moments and by their redox properties. The electronic spectra of all the complexes exhibit almost identical features consisting of two d–d bands at ca. 550 and 600 nm, one MLCT band at ca.400 nm, together with two π–π^* intra-ligand transitions at ca. 250 nm and ca.300 nm. Room temperature magnetic data range from μ = 2.7–3.0 BM indicates some super-exchange between the binuclear metal centers via bridging hydroxo/carboxylato groups. The X-ray crystal structure of the binuclear complex (5) revealed that it has a symmetric Mn^IIIN₂O₂ core bridged by a hydroxyl group. The X-ray analysis of the mononuclear complex (7) showed that the manganese-center possesses a distorted octahedral geometry. Electrochemical properties of hydroxo-bridged manganese(III) complexes (1–6) show identical features consisting of an irreversible and a quasi-reversible reduction corresponding to the Mn₂^III → Mn^IIMn^III → Mn^IIMn^II couples in the voltammogram. It was found that electron withdrawing substituents on the ligand result in easier reduction. Complex (7) displays an irreversible reduction at 0.08 V and a reversible oxidation at 0.45V assignable to the Mn^III → Mn^II reduction and Mn^III → Mn^IV oxidation, respectively. The carboxylate-bridged compound (8) exhibits two irreversible oxidations at 0.4 and 0.6 V, probably due to Mn₂^III → Mn^IIIMn^IV → Mn^IVMn^IV oxidations and shows a quasi-reversible reductive wave at −0.85 V, tentatively assigned to Mn₂^III → Mn^IIMn^III reduction.     

Surfactant tail length-dependent lipase activity profile in cationic water-in-oil microemulsions

The catalytic activity of Chromobacterium viscosum lipase (CV-lipase) was estimated across varying surfactant tail lengths (C-10-C-18) in water-in-oil (w/o) microemulsions of cationic surfactants containing four different hydroxyethyl-substituted head groups. An attempt to find a correlation, if any, between the activity of interfacially solubilized lipase and the varying surfactant tails was made for the first time in micellar enzymology. The second-order rate constant, k2, in lipase-catalyzed hydrolysis of p-nitrophenyl-n-hexanoate at pH 6.0 and 25 degrees C shows an improvement in enzyme activity (approximately 30-140%) across different head groups of amphiphiles with increasing tail lengths in varying solution compositions. Improvement of enzyme activity is prominent in ascending from C-10 to C-14/C-16, depending on the nature of polar head group. The hydrolytic activity of lipase in different surfactant (50 mM)/water/isooctane/n-hexanol with varying z= [alcohol]/[surfactant] (6.4 or 4.8) was amplified by 25-250% with increment in surfactant tail length in comparison with widely used cationic w/o microemulsions having solution compositions (z=16). As a notable outcome of this research, we found w/o microemulsions of 25 mM tetradecyltrimethylammonium bromide/water/isooctane/n-hexanol (z=8) producing the highest ever activity of lipase in any w/o microemulsions.     

Substituted m-phenylene bridges as strong ferromagnetic couplers for Cu(II)-bridge-Cu(II) magnetic interactions: new perspectives

Based on a combined theoretical-experimental study, we propose that substituted m-phenylene ligands (m-N-Phi-N) can act as tuneable strong ferromagnetic couplers connecting Cu(II) ions; a new complex presenting that bridge with J close to +15 cm(-1) has been suggested and synthesized.     

Low-macroscopic field emission from nanocrystalline Al doped SnO<Subscript>2</Subscript> thin films synthesized by sol–gel technique

We have observed low-macroscopic field electron emission from wide bandgap nanocrystalline Al doped SnO₂ thin films deposited on glass substrates. The emission properties have been studied for different anode-sample spacings and for different Al concentrations in the films. The turn-on field and approximate work function were calculated and we have tried to explain the emission mechanism from this. The turn-on field was found to vary in the range 5.6–7.5 V/μm for a variation of anode sample spacing from 80–120 μm. The turn-on field was also found to vary from 4.6–5.68 V/μm for a fixed anode-sample separation of 80 μm with a variation of Al concentration in the films 8.16–2.31%. The Al concentrations in the films have been measured by energy dispersive X-ray analysis. Optical transmittance measurement of the films showed a high transparency with a direct bandgap ∼3.98 eV. Due to the wide bandgap, the electron affinity of the film decreased. This, along with the nanocrystalline nature of the films, enhanced the field emission properties. PACS 81.20.Fw; 61.10.-i; 79.70.+q     

Specular X-ray reflectivity study of interfacial SiO2 layer in thermally annealed NiO/Si assembly

Present report details an analysis of X-ray reflectivity (XRR) for solution processed NiO thin films on Si (100) substrates. The films were annealed at 700–1,000 °C for 1 h in air. XRR data indicated growth of SiO₂ layer from ~8 nm at 700 °C to ~66 nm at 1,000 °C along with significant variation of electron density profile. X-ray photoelectron spectroscopy and X-ray diffraction studies were used as supporting studies for phase purity and oxidation states of the NiO thin films as well as interfacial SiO₂ layer.     

Analysis of short-pulse laser photon transport through tissues for optical tomography

We describe a method for analyzing short-pulse laser propagation through tissues for the detection of tumors and inhomogeneities in tissues with the goal of developing a time-resolved optical tomography system. Traditional methods for analyzing photon transport in tissues usually involve the parabolic or diffusion approximation, which implies infinite speed of propagation of the optical signal. To overcome such limitations we calculate the transmitted and reflected intensity distributions, using the damped-wave hyperbolic P(1) and the discrete-ordinates methods, for a wide range of laser, tissue, and tumor parameters. The results are compared with the parabolic diffusion P(1) approximation.     

Carbon-13 NMR signals of some benzodiazepine drugs

Some carbon-13 NMR signal assignments of diazepam, flurazepam, clonazepam and chlordiazepoxide have been revised and the assignments of nitrazepam are reported. The assignments of the various resonances were made by considering the changes in chemical shifts produced by the change of substituents and also by comparison with the chemical shifts of model compounds.     

Lattice dynamical calculation of the second Grüneisen constant of CsBr

The second order Grüneisen constant constitutes an additional measure of the anharmonicity in a solid (the Grüneisen constant itself being the first measure). This quantity and the corresponding second mode-Grüneisen parameters are calculated for CsBr using a modified rigid ion model of lattice dynamics. The model parameters are deduced from the three elastic constants and the long wavelength optical mode frequencies. Using the first and second order pressure dependences of these physical observables, the individual second mode-Grüneisen parameters are obtained as a function of wave vector. The temperature variation of the second Grüneisen constant is then deduced in a quasi-harmonic approximation. The second Grüneisen constant is also calculated from available thermodynamic data and is in reasonable agreement with the present theoretical prediction.     

Is multiscaling an artifact in the stochastically forced Burgers equation?

We study turbulence in the one-dimensional Burgers equation with a white-in-time, Gaussian random force that has a Fourier-space spectrum approximately 1/k, where k is the wave number. From very high-resolution numerical simulations, in the limit of vanishing viscosity, we find evidence for multiscaling of velocity structure functions which cannot be falsified by standard tests. We find a new artifact in which logarithmic corrections can appear disguised as anomalous scaling and conclude that bifractal scaling is likely.     

Jahn–Teller coupled charge density wave in a double exchange system

In a two orbital model, we formulate Jahn–Teller coupled charge density wave in one electron per lattice site limit. Softening of Jahn–Teller phonons corresponding to distortion modes Q₂ or Q₃ associated with perfect nesting of Fermi surface leads to this instability at low temperature. The gap equation for charge density wave state and its dependences on electron–lattice coupling are calculated explicitly when any one of the Jahn–Teller modes is excited cooperatively. We find that the Q₂ distortion mode yields lowest free energy. Effect of electron–lattice interaction on collective mode, such as amplitude mode, is more pronounced when the excited mode is Q₂.