Highly Birefringent Microstructure Fiber with Zero Dispersion Wavelength at 0.64 Micrometer

Abstract

In this article, we have designed a microstructure fiber, which consists of elliptical air holes at the core region. We have investigated its optical properties using finite difference time domain method. The fundamental mode of the proposed microstructure fiber can induce very high birefringence. It has been realized that the value of birefringence is mainly decided by the shape of the air holes present in the first and second rings. The zero dispersion wavelengths of both fast and slow axes have been shifted to 0.64 micrometer. The proposed birefringent microstructure fiber may be useful in optical communication and sensors.     

Sensitive method for the determination of paricalcitol by liquid chromatography and mass spectrometry and its application to a clinical pharmacokinetic study

A highly sensitive, specific and rapid LC‐ESI‐MS/MS method has been developed and validated for the quantification of paricalcitol (PAR) in human plasma (500 μL) using paricalcitol‐d₆ (PAR‐d₆) as an internal standard (IS) as per regulatory guidelines. A liquid–liquid extraction method was used to extract the analyte and IS from human plasma. Chromatography was achieved on Zorbax SB C₁₈ column using an isocratic mobile phase in a gradient flow. The total chromatographic run time was 6.0 min and the elution of PAR and PAR‐d₆ occurred at ~2.6 min. A linear response function was established for the range of concentrations 10–500 pg/mL in human plasma. The intra‐ and inter‐day accuracy and precision values for PAR met the acceptance criteria. The validated assay was applied to quantitate PAR concentrations in human plasma following oral administration of 4 µg capsules to humans. Copyright © 2014 John Wiley & Sons, Ltd.     

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.     

Thia- und Dithia-cycloalkane und die Spaltung einiger gesättigter Heterocyclen mit Methyljodid

Zusammenfassung Die 8- und 9-gliedrigen Thia-cycloalkane und die dimeren 14-, 16- und 18-gliedrigen Ringsulfide wurden aus den entsprechenden ,-Dibromalkanen und Natriumsulfid in hochverdünnter alkoholischer Lösung erstmalig dargestellt und charakterisiert. Die Beweisführung für die Struktur der Monomeren erfolgte durch Ringspaltung mit Methyljodid und Identifizierung der entstandenen ,-Dijodalkane.Es wird gezeigt, daß die Ringspaltungsmethode mit Methyljodid unter Herauslösung der gesamten C-Kette auch auf gewisse gesättigte O- und N-Heterocyclen anwendbar ist. Tetrahydrofuran, 1,6-Epoxyhexan und 1,4-Dioxan sowie der Trimethyleniminring werden sämtlich in verschiedenem Ausmaß gespalten, nicht aber die Polymethylenimine mit 4 bis 7 C-Atomen. Im spirocyclischen N,N-Hexamethylen-piperidiniumjodid wird jedoch der 7-gliedrige Ring gesprengt. Piperazin wird nicht angegriffen, wohingegen die Ringhomologen, 1,5-Diaza-cyclooctan und 1,10-Diaza-cyclooctadecan der Spaltung zugänglich sind.Soweit untersucht, werden Benzoyl und p-Toluolsulfonyl am Stickstoff allgemein durch Methyl verdrängt, p-Nitrophenyl und o,p-Dinitrophenyl werden aber nicht ausgetauscht.Mit 4 Abbildungen.     

Quantum chemical studies on hydrogen adsorption in carbon-based model systems: role of charged surface and the electronic induction effect

Quantum chemical studies on the molecular hydrogen adsorption in a six-membered carbon ring has been undertaken to mimic the adsorption process in carbon nanotubes, considering the fact that the six-membered carbon ring is found to be one of the basic units of the carbon nanotubes and fullerenes. Our results reveal that the carbon surface as such is not a good candidate for hydrogen adsorption but a charged surface created by doping of an alkali metal atom can play an important role for the improvement in adsorption of molecular hydrogen. The strength of hydrogen interaction as well as the number of hydrogen molecules that can be adsorbed on the system is found to depend on the nature of the cation doped in the system. We have also studied the role of electronic induction by substituting different functional groups in the model system on the hydrogen adsorption energy. The results demonstrate that the binding energy of the cation with the carbon surface as well as the hydrogen adsorption energy can be tuned significantly through the use of suitable substituents. In addition, we have shown that the extended planar or the curved carbon surface of the coronene system alone may not be suitable for an effective molecular hydrogen adsorption. In essence, our results reveal that the ionic surface with a significant degree of curvature will enhance the hydrogen adsorption effectively.     

Design and synthesis of a unique ditopic macrocyclic fluorescent receptor containing furan ring as a spacer for the recognition of dicarboxylic acids

A macrocyclic fluorescent receptor was designed and synthesised and the binding study with three different types of dicarboxylic acids was performed with the receptor being found to have appreciable association constants. Downfield shifts of specific amide protons in 1:1 binding by ¹H NMR and the quenching in the fluorescence spectra reveal strong binding and thus unambiguously support the complexation of the receptor 1 with dicarboxylic acids.     

Indium-mediated vic-diallylation/propargylation of phenacyl bromides: a facile synthesis of 4-arylocta-1,7-dien-4-ol derivatives

Phenacyl bromides undergo smooth vic-diallylation and dipropargylation with allyl and propargyl indium reagents generated in situ from metallic indium and allyl or propargyl bromide to produce 4-arylocta-1,7-dien-4-ol derivatives in good yields. Phenacyl chloride and azide also participated effectively in bis-allylation. Similar results are also obtained from in situ generated allyl or propargyl zinc bromide.     

A one-dimensional energy diffusion approach to multidimensional dynamical processes in the condensed phase

We propose a generalized one-dimensional energy diffusion approach for describing the dynamics of multidimensional dynamical processes in the condensed phase. On the basis of a formalism originally due to Zwanzig, we obtain a one-dimensional kinetic equation for a properly selected relevant dynamical quantity and derive new analytical results for the dynamics of a multidimensional electron-transfer process, nonequilibrium solvation, and diffusive escape from a potential well. The calculated results for electron-transfer reactions in solvent-separated and contact ion pair systems are found to be in good agreement with the experimental results. We are able to explain the rate of the electron-transfer reaction using much smaller and reasonable values of the solvent reorganization energy in contrast to earlier works that had to use a much larger value. The proposed theory is not only conceptually simpler than the conventional approaches but is also free from many of their limitations. More importantly, it provides a single theoretical framework for describing a wide class of dynamical phenomena.     

Micellar shape transition under dilute salt-free conditions: promotion and self-fluorescence monitoring of stimuli-responsive viscoelasticity by 1- and 2-naphthols

Effect of 1 and 2-naphthols on the shape transition of cetyl trimethylammonium bromide (CTAB) and cetylpyridinium bromide (CPB) micelles are studied. Stimuli-responsive viscoelastic gels of long wormlike micelles are formed at low surfactant concentrations in the presence of neutral naphthols, where H-bonding plays a key role in micellar shape transition in the absence of any charge screening. Micelle-embedded naphthols also act as novel self-fluorescence probes for monitoring viscoelasticity of the system as a function of applied shear. 1H NMR study shows that the solubilization sites of naphthols in the micelle are located near the surface. While UV absorption and Fourier transform infrared studies confirm the presence of intermolecular H-bonds in micelle embedded naphthols, transmission electron micrographs of vacuum-dried samples at room temperature demonstrate the transition in shape from sphere to rodlike micelles.     

Effect of pressure on colloidal behavior in hydrothermal water

The pressure dependence of the colloidal phenomena of nanoparticles in hydrothermal water was investigated by both experiment and theory. Dynamic light scattering experiments show that diamond nanoparticles, which are highly stable in ambient water, easily aggregate in high-temperature and high-pressure water. Although the stability of nanoparticles in ambient pure water does not depend on pressure, it is interestingly found that at constant temperature particles aggregate faster in the hydrothermal regime when the pressure is higher. A theoretical interpretation is proposed to predict the stability of colloids in water as a function of temperature and pressure. Numerical analysis shows that the repulsive interparticle potential barrier, which stabilizes particles in the dispersion, decreases dramatically in high-temperature and high-pressure water. The decrease in the potential barrier arises from the temperature and the pressure dependencies of the dielectric constant (epsilon) and the ion product (p K w) of water. Numerical analysis shows that the pressure dependence of epsilon is negligible in the temperature range of 20-300 degrees C, whereas the pressure dependence of p K w is significant at temperatures of T > 150 degrees C. The theory reveals that the pressure dependence of the rate of size increment in the hydrothermal regime results from the pressure dependence of p K w. An increase in pressure in the hydrothermal water enhances the ionization of water molecules which reduces the surface potential of the particles. This effect lowers the interparticle repulsive potential barrier, which accelerates aggregation of the particles.