Synthesis, characterization and studies on the nonlinear optical parameters of hydrazones

Three hydrazones, 2-(4-methylphenoxy)-N′-[(1E)-(4-nitrophenyl)methylene]acetohydrazide (compound-1), 2-(4-methylphenoxy)-N′-[(1E)-(4-methylphenyl)methylene]acetohydrazide ((compound-2) and N′-{(1E)-[4-(dimethylamino)phenyl]methylene}-2-(4-ethylphenoxy) acetohydrazide(compound-3) were synthesized and their third order nonlinear optical properties were investigated using a single beam z-scan technique with nanosecond laser pulses at 532 nm. Open aperture data obtained from the three compounds indicates two photon absorption at this wavelength. The nonlinear refractive index n₂, the nonlinear absorption coefficient β, the magnitude of the effective third order susceptibility χ⁽³⁾, the second order hyperpolarizability γ_h and the coupling factor ρ have been estimated. The values obtained are comparable with the values obtained for 4-methoxy chalcone derivatives and dibenzylidene acetone derivatives. Among the compounds studied, compounds-1 and 3 exhibited the better optical power limiting behaviour at 532 nm. Our studies suggest that compounds-1, 2 and 3 are potential candidates for optical device applications such as optical limiters and optical switches.     

Electronic structure, phonons, and dielectric anomaly in ferromagnetic insulating double pervoskite La2NiMnO6

Using first-principles density functional calculations, we study the electronic and magnetic properties of the ferromagnetic insulating double perovskite compound La2NiMnO6, which has been reported to exhibit an interesting magnetic field sensitive dielectric anomaly as a function of temperature. Our study reveals the existence of very soft infrared active phonons that couple strongly with spins at the Ni and Mn sites through modification of the superexchange interaction. We suggest that these modes are the origin for the observed dielectric anomaly in La2NiMnO6.     

Fluoride‐Catalyzed Deblocking: A Route to Polymeric Urethanes

We report a fluoride‐catalyzed deblocking of urethanes as “blocked” isocyanates. Organic and inorganic sources of fluoride ion proved effective for deblocking urethanes and for converting polyurethanes to small molecules. Distinct from conventional deblocking chemistry involving organometallic compounds and high temperatures, the method we describe is metal‐free and operates at or slightly above room temperature. The use of fluorescent blocking agents enabled visual and spectroscopic monitoring of blocking/deblocking reactions, and the selected conditions proved applicable to urethanes containing a variety of blocking groups. The method additionally enabled a one pot deblocking and polymerization with α,ω‐diols. Overall, this deblocking/polymerization strategy offers a convenient and efficient solution to problems that have limited the breadth of applications of polyurethane chemistry.     

Validation of an LC–MS/MS Method for Simultaneous Detection of Five Selective KCNQ Channel Openers: ICA-27243, ML-213, PF-05020182, SF-0034 and Flupirtine in Mice Plasma and its Application to a Pharmacokinetic Study in Mice

A sensitive and rapid LC–MS/MS method was developed and validated for the simultaneous quantitation of five selective KCNQ channel openers, namely ICA-27243, ML-213, PF-05020182, SF-0034 and flupirtine in mice plasma as per regulatory guideline. The analytes and the internal standard (IS; flupirtine-d ₄ ) were extracted from 50 µL mice plasma by liquid–liquid extraction, followed by chromatographic separation using an Atlantis C₁₈ column with an isocratic mobile phase comprising 0.2% formic acid: acetonitrile (20:80, v/v) at a flow rate of 0.6 mL min^?1 within 2.5 min. Detection and quantitation was done by multiple reaction monitoring on a triple quadrupole mass spectrometer following the transitions: m/z 268.9 → 140.8, 258.1 → 95.1, 367.2 → 269.1, 322.2 → 248.2, 305.7 → 196.4 and 309.1 → 196.1 for ICA-27243, ML-213, PF-05020182, SF-0034, flupirtine and the IS, respectively, in the positive ionization mode. The calibration curves were linear from 1.00 to 2008 ng mL^?1 for all the analytes with r² ≥ 0.99. The intra- and inter-batch accuracy and precision (% CV) across quality controls varied from 90.0 to 113 and 2.64 to 13.0; 93.8 to 114 and 3.15 to 14.9%, respectively, for all the analytes. Analytes were found to be stable under different stability conditions. The method was applied to a pharmacokinetic study in mice.     

Size dependence of structural, electronic, elastic, and optical properties of selenium nanowires: a first-principles study

We have studied the structural, elastic, and optical properties of selenium nanowires, as well as bulk selenium, by performing first-principles density functional theory calculations. The nanowires are structurally similar to bulk trigonal Se, in that they consist of hexagonal arrays of helices, though there is a slight structural rearrangement in response to the finite size of the nanowires. These small structural changes result in Young's modulus decreasing slightly for progressively thinner nanowires. However, there is a significant effect on electronic structure and optical properties. The thinner the nanowire, the greater the band gap, and the greater the anisotropy in optical conductivity. The latter is due to the effects of finite size being much more marked for the case where the electric field is polarized perpendicular to the helical axis, than in the case where the polarization is parallel to c. For the case of bulk Se, we obtain good agreement with experimental data on the structure, elastic constants, and dielectric function.     

Structure of incommensurate gold sulfide monolayer on Au(111)

We develop an atomic-scale model for an ordered incommensurate gold sulfide (AuS) adlayer which has previously been demonstrated to exist on the Au(111) surface, following sulfur deposition and annealing to 450 K. Our model reproduces experimental scanning tunneling microscopy images. Using state-of-the-art Wannier-function-based techniques, we analyze the nature of bonding in this structure and provide an interpretation of the unusual stoichiometry of the gold sulfide layer. The proposed structure and its chemistry have implications for related S-Au interfaces, as in those involved in self-assembled monolayers of thiols on Au substrates.     

Ultrafast nonlinear optical properties of dye-doped PMMA discs irradiated by 40 fs laser pulses

The two-photon absorption (TPA) characteristics of PMMA discs doped with three different dyes were studied using an fs-pulsed Ti-Sapphire laser as the pump source, and employing the open-aperture Z-scan technique. TPA cross-sections obtained for PMMA doped with the dyes PM597, DCM and rhodamine 6G–rhodamine B (co-doped) were found to be equal to 24.7, 33.3 and 32.3 GM, respectively (1 GM=10^?50 cm⁴ s phot^?1 mol^?1). Furthermore, two-photon fluorescence was measured for the samples containing DCM and rhodamine 6G–rhodamine B (co-doped). Compared to the one-photon fluorescence spectrum, the peaks in the two-photon fluorescence spectrum were red shifted and the extent of red shift increased with increasing doping concentration. We have also observed that the red shift in the two-photon fluorescence peak of the samples in the solid form is much larger than that in the solution state. This phenomenon could be explained by a twisted intra-molecular charge transfer model.     

Simulation and experimental characterization of Raman/EDFA hybrid amplifier with enhanced performance

We present simulation and experimental characterization of a hybrid amplifier comprising of a Raman amplifier and an erbium doped fiber (EDF) amplifier, with enhanced performance. The incorporation of a pumped EDF section in a fiber Raman amplifier (FRA) employing a dispersion compensating fiber is demonstrated to provide superior performance than a sole FRA system. The hybrid amplifier is characterized in terms of single channel gain and noise figure, and the results of measurements are shown to be in close agreement with the simulated results. Polarization-dependent gain (PDG) and multi-channel measured and simulated gain characterization of the Raman/EDFA hybrid amplifier are also presented.     

Facile approach to diverse range of 1,3-diaza-heterocycles: angular/linear selectivity paradigm and a remarkable intramolecular methyl migration

Starting from cyclic anhydrides and tert-butyl 2-aminobenzylcarbamate, simple and efficient synthesis of diverse range of kinetically controlled angular and thermodynamically controlled linear tricyclic and tetracyclic 1,3-diaza-heterocycles have been described via the intramolecular cyclizations of the corresponding imides/anilic acid esters. The effect of imide stability on the angular/linear product selectivity has also been described. The kinetically controlled angular products were successfully transformed to the corresponding thermodynamically controlled linear products by refluxing in methanol or methanol and acetic acid mixture. An interesting in situ 1,2-intramolecular methyl group migration has also been described.