Supercritical fluid chromatography tandem mass spectrometry employed with evaporation-free liquid–liquid extraction for the rapid analysis of cinnarizine in rat plasma

Cinnarizine is a weak base, which can produce supersaturation and precipitation during gastrointestinal transit, affecting its absorption in vivo. Therefore, it is necessary to investigate whether the oral bioavailability of cinnarizine can be improved after co-administration with precipitation inhibitors or not. In order to evaluate the pharmacokinetic behavior of cinnarizine in rats, a simple, rapid, sensitive, and environmentally friendly supercritical fluid chromatography-tandem mass spectrometric method was established and validated. In this method, flunarizine, a structural analogue of cinnarizine, was selected as the internal standard, and cinnarizine was extracted from rat plasma using evaporation-free liquid–liquid extraction method. The analytes were separated on a Torus 1-AA column (3.0 mm × 100 mm, 1.7 μm) within 2.0 min, using a gradient elution procedure. The transitions of cinnarizine and flunarizine were m/z 369.1 → 167.1 and m/z 405.1 → 203.1, respectively. Cinnarizine showed good linear correlation in the range of 1–500 ng/ml with a lower limit of quantification of 1 ng/ml. The intra- and interday precision and accuracy of all quality control samples were within ±15%. This high-throughput, accurate, sensitive, and reproducible method has been successfully applied to study the effects of the precipitation inhibitor cinnarizine on the pharmacokinetics in rats.     

Concerted effect of boron and porosity on shear thickening behavior of hybrid mesoporous silica dispersions

In the present work, the influence of porosity and boron on shear thickening behavior of hybrid mesoporous silica has been studied. Three different levels of boron modification were performed by varying the molar composition of boric acid viz., 1.5 mmol, 2.5 mmol, and 3.5 mmol in a co-condensation approach. The incorporation of boron in mesoporous silica network was confirmed by various techniques such as Fourier transform infra-red (FTIR), and ¹¹B solid- state nuclear magnetic resonance (NMR) spectroscopy. The morphology and particle size were confirmed by using scanning and transmission electron microscopy. To evaluate the effect of boron and porosity on the shear thickening behavior, dispersions were prepared from mesoporous boron- modified silica (MSiB), control mesoporous silica (MSi), non-porous boron-modified silica (SiB), and control non-porous silica (Si) in polyethylene glycol. The shear thickening behavior was studied using steady shear rheology. The dispersion prepared from different loadings of synthesized MSiB containing 1.5 mmol boron showed more than 16 times increase in viscosity (657.7 Pa.s) compared to that of MSi (39.2 Pa.s) at a fairly low volume fraction (φ = 0.15) of silica. It is expected that the highly ordered mesoporous architecture of hybrid silica has improved the interaction between the particle and the dispersing medium through hydrogen bonding. The porous morphology of the hybrid mesoporous silica as well as the incorporation of boron in the silica network favors the formation of a frictional contact network, and a transition from continuous shear thickening (CST) to discontinuous shear thickening (DST) behavior was observed. Therefore, silica prepared via incorporation of boron as well as porosity can be material of interest in variety of applications, for example, soft body armors, sporting goods, and shear thickening electrolytes for high impact resistant batteries.     

Kinetic Behavior of Quaternary Ammonium Hydroxides in Mixed Methane and Carbon Dioxide Hydrates

This study evaluates the kinetic hydrate inhibition (KHI) performance of four quaternary ammonium hydroxides (QAH) on mixed CH₄ + CO₂ hydrate systems. The studied QAHs are; tetraethylammonium hydroxide (TEAOH), tetrabutylammonium hydroxide (TBAOH), tetramethylammonium hydroxide (TMAOH), and tetrapropylammonium hydroxide (TPrAOH). The test was performed in a high-pressure hydrate reactor at temperatures of 274.0 K and 277.0 K, and a concentration of 1 wt.% using the isochoric cooling method. The kinetics results suggest that all the QAHs potentially delayed mixed CH₄ + CO₂ hydrates formation due to their steric hindrance abilities. The presence of QAHs reduced hydrate formation risk than the conventional hydrate inhibitor, PVP, at higher subcooling conditions. The findings indicate that increasing QAHs alkyl chain lengths increase their kinetic hydrate inhibition efficacies due to better surface adsorption abilities. QAHs with longer chain lengths have lesser amounts of solute particles to prevent hydrate formation. The outcomes of this study contribute significantly to current efforts to control gas hydrate formation in offshore petroleum pipelines.     

Color Stabilization of Apulian Red Wines through the Sequential Inoculation of Starmerella bacillaris and Saccharomyces cerevisiae

Mixed fermentation using Starmerella bacillaris and Saccharomyces cerevisiae has gained attention in recent years due to their ability to modulate the qualitative parameters of enological interest, such as the color intensity and stability of wine. In this study, three of the most important red Apulian varieties were fermented through two pure inoculations of Saccharomyces cerevisiae strains or the sequential inoculation of Saccharomyces cerevisiae after 48 h from Starmerella bacillaris. The evolution of anthocyanin profiles and chromatic characteristics were determined in the produced wines at draining off and after 18 months of bottle aging in order to assess the impact of the different fermentation protocols on the potential color stabilization and shelf-life. The chemical composition analysis showed titratable acidity and ethanol content exhibiting marked differences among wines after fermentation and aging. The 48 h inoculation delay produced wines with higher values of color intensity and color stability. This was ascribed to the increased presence of compounds, such as stable A-type vitisins and reddish/violet ethylidene-bridge flavonol-anthocyanin adducts, in the mixed fermentation. Our results proved that the sequential fermentation of Starmerella bacillaris and Saccharomyces cerevisiae could enhance the chromatic profile as well as the stability of the red wines, thus improving their organoleptic quality.     

Comparative Studies of Selected Criteria Enabling Optimization of the Extraction of Polar Biologically Active Compounds from Alfalfa with Supercritical Carbon Dioxide

The aim of this research was to provide crucial and useful data about the selection of the optimization criteria of supercritical carbon dioxide extraction of alfalfa at a quarter-technical plant. The correlation between more general output, including total phenolics and flavonoids content, and a more specified composition of polar constituents was extensively studied. In all alfalfa extracts, polar bioactive constituents were analyzed by both spectrometric (general output) and chromatographic (detailed output) analyses. Eight specific phenolic acids and nine flavonoids were determined. The most dominant were salicylic acid (221.41 µg g⁻¹), ferulic acid (119.73 µg g⁻¹), quercetin (2.23 µg g⁻¹), and apigenin (2.60 µg g⁻¹). For all seventeen analyzed compounds, response surface methodology and analysis of variance were used to provide the optimal conditions of supercritical fluid extraction for each individual constituent. The obtained data have shown that eight of those compounds have a similar range of optimal process parameters, being significantly analogous for optimization based on total flavonoid content.     

Reactivities of mixed organozinc and mixed organocopper reagents. Part 13 Kinetic study for phosphine‐catalyzed acylation of alkylarylzincs and effect of residual group on the transfer rate of alkyl group

Kinetics of reactions of di‐n‐butylzinc, n‐Bu₂Zn, and mixed n‐butyl(substituted phenyl)zinc reagents and n‐Bu(functional group (FG)?C₆H₄)Zn with benzoyl chloride in the presence of tri‐n‐butylphosphine have been investigated. Reaction rates of transferable n‐butyl group have been determined in tetrahydrofuran at 0 °C to compare the transfer rate of n‐butyl group in homo and mixed diorganozincs. Rate law is consistent with a third‐order reaction, which is first order in diorganozinc, benzoyl chloride, and n‐Bu₃P, and a mechanism was proposed. The lower reaction rate of n‐BuPhZn than that of n‐Bu₂Zn and negative reaction constant in Hammett plot are in accordance with the carbanionic charge of transferable n‐butyl group in the acylation reaction. These findings support the hypothesis that the reaction rate of transferable group, R_T, changes depending upon the residual group, R_R, in R_RR_TZn reagents. Copyright © 2016 John Wiley & Sons, Ltd.     

Secondary-flow-aided single-train elastic-inertial focusing in low elasticity viscoelastic fluids

Elastic-inertial focusing has attracted increasing interest in recent years due to the three-dimensional (3D) single-train focusing ability it offers. However, multi-train focusing, instead of single-train focusing, was observed in viscoelastic fluids with low elasticity as a result of the competition between inertia effect and viscoelasticity effect. To address this issue, we employed the secondary flow to facilitate single-train elastic-inertial focusing in low elasticity viscoelastic fluids. A three-section contraction-expansion channel was designed to induce the secondary flow to pinch the multiplex focusing trains into a single one exactly at the channel centerline. After demonstrating the focusing process and mechanism in our device, we systematically explored and discussed the effects of particle diameter, operational flow rate, polymer concentration, and channel dimension on particle focusing performances. Our device enables single-train focusing of particles in viscoelastic fluids with low elasticity, and offers advantages of planar single-layer structure, and sheathless, external-field free operation.     

Positive numerical splitting method for the Hull and White 2D Black–Scholes equation

We consider the locally one‐dimensional backward Euler splitting method to solve numerically the Hull and White problem for pricing European options with stochastic volatility in the presence of a mixed derivative term. We prove the first‐order convergence of the time‐splitting. The parabolic equation degenerates on the boundary x = 0 and we apply a fitted finite volume scheme to the equation to resolve the degeneracy and derive the fully discrete problem as we also investigate the discrete maximum principle. Numerical experiments illustrate the efficiency of our difference scheme. © 2014 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 31: 822–846, 2015     

Determination of conditional stability constants for some divalent transition metal ion‐EDTA complexes by electrospray ionization mass spectrometry

Conditional stability constants of coordination complexes comprising divalent transition metals, Cu²⁺, Ni²⁺, Zn²⁺, Co²⁺, and ethylenediaminetetraacetic acid (EDTA) were determined utilizing electrospray ionization mass spectrometry. The deviation of signal response of a reference complex was monitored at addition of a second metal ion. The conditional stability constant for the competing metal was then determined through solution equilibria equations. The method showed to be applicable to a system where Co²⁺ and Zn²⁺ competed for EDTA at pH 5. When Cu²⁺ and Ni²⁺ competed for EDTA, the equilibrium changed over time. This change was shown to be affected in rate and size by the type of organic solvent added. In this work, 30% of either methanol or acetonitrile was used. It was found that if calibration curves are prepared for both metal complexes in solution and the measurements are repeated with sufficient time space, any change in equilibrium of sample solutions will be discovered. Copyright © 2014 John Wiley & Sons, Ltd.     

Electrochemically Generated Nanoparticles of Halogen‐Bridged Mixed‐Valence Binuclear Metal Complex Chains

Spherical nanoparticles composed of MMX chains can be made by a polymerization strategy driven by electrochemical processes. In particular, the [Pt₂(MeCS₂)₄I₂] (MMI₂) dimetal subunit is employed as a monomer for the formation of [Pt₂(MeCS₂)₄I]_n spherical nanostructures on surfaces. We have paid particular attention to elucidating the general mechanism of the deposition process on the basis of in situ electrochemical measurements. The reduction of MMI₂ to give the electrodeposition of nanostructures agrees well with formation of the reduced [MMI₂]^? species followed by a disproportionation mechanism mediated by iodide anions. The chemical composition of the particles was determined by energy‐dispersive X‐ray spectroscopy (EDX) and X‐ray photoelectron spectroscopy (XPS) to reveal the MMI₂ polymer.