Determination of three antidepressants in urine using simultaneous derivatization and temperature‐assisted dispersive liquid–liquid microextraction followed by gas chromatography–flame ionization detection

This paper presents a fast and simple method for the extraction, preconcentration and determination of fluvoxamine, nortriptyline and maprotiline in urine using simultaneous derivatization and temperature‐assisted dispersive liquid–liquid microextraction (TA‐DLLME) followed by gas chromatography–flame ionization detection (GC‐FID). An appropriate mixture of dimethylformamide (disperser solvent), 1,1,2,2‐tetrachloroethane (extraction solvent) and acetic anhydride (derivatization agent) was rapidly injected into the heated sample. Then the solution was cooled to room temperature and cloudy solution formed was centrifuged. Finally a portion of the sedimented phase was injected into the GC‐FID. The effect of several factors affecting the performance of the method, including the selection of suitable extraction and disperser solvents and their volumes, volume of derivatization agent, temperature, salt addition, pH and centrifugation time and speed were investigated and optimized. Figures of merit of the proposed method, such as linearity (r² > 0.993), enrichment factors (820–1070), limits of detection (2–4 ng mL^?1) and quantification (8–12 ng mL^?1), and relative standard deviations (3–6%) for both intraday and interday precisions (concentration = 50 ng mL^?1) were satisfactory for determination of the selected antidepressants. Finally the method was successfully applied to determine the target pharmaceuticals in urine. Copyright © 2014 John Wiley & Sons, Ltd.     

Effect of Partially Hydrolyzed Kappa-Casein on Physicochemical and Sensory Properties of Heated Milk

The chemical, physical, and sensory characteristics of renneted skim milk (RSM) containing partially hydrolyzed κ-casein were assessed and compared with skim milk (control). Rennet was added to heated milk (60°C for 15 minutes) at seven concentrations from 0.1 to 0.7 mL rennet/100 mL milk followed by heating to 63°C for 30 minutes in order to inactivate the rennet. The RSM samples had higher viscosity as well as whiter, yellower, and greener color in comparison with control sample. The range of size distribution of casein aggregates was larger than that of skim milk, while being within the range of fat mimetics.     

Challenges in the indirect quantitation of acyl‐glucuronide metabolites of a cardiovascular drug from complex biological mixtures in the absence of reference standards

This paper describes the quantitation of acyl‐glucuronide metabolites (M26 and M5) of a cardiovascular‐drug (torcetrapib) from monkey urine, in the absence of their reference standards. LC/MS/MS assays for M1 and M4 (aglycones of M26 and M5, respectively) were characterized from normal and base‐treated urine, as their respective reference standards were available. The in vivo study samples containing M26 and M5 were treated with 1 n sodium hydroxide to hydrolyze them to their respective aglycones. The study samples were assayed for M1 and M4 before and after alkaline hydrolysis and the difference in the concentrations provided an estimate of the urinary levels of M26 and M5. Prior to the main sample analysis, conditions for alkaline hydrolysis of the glucuronides were optimized by incubating pooled study samples. During incubations, a prolonged increase in M4 levels over time was observed, which is inconsistent with the base‐hydrolysis of an acyl‐glucuronide (expected to hydrolyze rapidly). Possible interference of the metabolite M9 (an ether‐glucuronide metabolite isobaric to M4) was investigated to explain this observation using chromatographic and wet‐chemistry approaches. The strategies adopted herein established that the LC/MS/MS assay and our approach were reliable. The metabolite exposure was then correlated to toxicological observations to gain initial insights into the physiological role of these metabolites. Copyright © 2009 John Wiley & Sons, Ltd.     

Silica-bonded S-sulfonic acid: an efficient and recyclable solid acid catalyst for the three-component synthesis of α-amino nitriles

Silica-bonded S-sulfonic acid (SBSSA) is employed as a recyclable catalyst for the synthesis of α-amino nitriles. These syntheses were performed via a one-pot three-component condensation of aldehydes, amines, and trimethylsilyl cyanide under mild reaction conditions at room temperature.     

Hiscotropic rearrangements: hybrids of electrocyclic and sigmatropic reactions

An unusual reaction manifold for cyclopropylcarbinyl cations, uncovered using B3LYP and MP2 calculations, is described. This reaction is a hybrid of a [1,2] sigmatropic hydrogen shift and a two-electron electrocyclic ring opening. These two processes occur through a single transition structure (i.e., they are concerted), although they are not synchronous. We call these reactions "hiscotropic" rearrangements. The potential energy surfaces for these reactions are often complicated, in some cases involving flat plateaus and bifurcations. Torquoselectivity occurs in some cases as a result of favorable orbital interactions between the breaking C-C and C-H bonds.     

Dynamics of water droplets detached from porous surfaces of relevance to PEM fuel cells

The detachment of liquid droplets from porous material surfaces used with proton exchange membrane (PEM) fuel cells under the influence of a cross-flowing air is investigated computationally and experimentally. CCD images taken on a purpose-built transparent fuel cell have revealed that the water produced within the PEM is forming droplets on the surface of the gas-diffusion layer. These droplets are swept away if the velocity of the flowing air is above a critical value for a given droplet size. Static and dynamic contact angle measurements for three different carbon gas-diffusion layer materials obtained inside a transparent air-channel test model have been used as input to the numerical model; the latter is based on a Navier–Stokes equations flow solver incorporating the volume of fluid (VOF) two-phase flow methodology. Variable contact angle values around the gas–liquid–solid contact-line as well as their dynamic change during the droplet shape deformation process, have allowed estimation of the adhesion force between the liquid droplet and the solid surface and successful prediction of the separation line at which droplets loose their contact from the solid surface under the influence of the air stream flowing around them. Parametric studies highlight the relevant importance of various factors affecting the detachment of the liquid droplets from the solid surface.     

Nonlinear Triple Product $$A^{*}B + B^{*}A$$ for Derivations on $$\ast$$ -Algebras

Mathematical Notes - Let $$\mathcal{A}$$ be a prime $$\ast$$ -algebra. In this paper, assuming that $$\Phi:\mathcal{A}\to\mathcal{A}$$ satisfies $$\Phi(A\diamond B \diamond C)=\Phi(A)\diamond B...     

An experimental study on the effect of air bubble injection on the flow induced rotational hub

Modification of shear stress due to air bubbles injection in a rotary device was investigated experimentally. Air bubbles inject to the water flow crosses the neighbor of the hub which can rotate just by water flow shear stresses, in this device. Increasing air void fraction leads to decrease of shear stresses exerted on the hub surface until in high void fractions, the hub motion stopped as observed. Amount of skin friction decrease has been estimated by counting central hub rotations. Wall shear stress was decreased by bubble injection in all range of tested Reynolds number, changing from 50,378 to 71,238, and also by increasing air void fraction from zero to 3.06%. Skin friction reduction more than 85% was achieved in this study as maximum measured volume of air fraction injected to fluid flow while bubbles are distinct and they do not make a gas layer. Significant skin friction reduction obtained in this special case indicate that using small amount of bubble injection causes large amount of skin friction reduction in some rotary parts in the liquid phases like as water.     

A large data existence result for the stationary Boltzmann equation in a cylindrical geometry

AnL ¹-existence theorem is proved for the nonlinear stationary Boltzmann equation with hard forces and no small velocity truncation—only the Grad angular cut-off-in a setting between two coaxial rotating cylinders when the indata are given on the cylinders.