Flow-injection chemiluminescent determination of metoclopramide hydrochloride in pharmaceutical formulations and biological fluids using the [Ru(dipy)(3)(2+)]-permanganate system

A flow-injection (FI) methodology using (2,2′-dipyridyl) ruthenium(II) [Ru(dipy)₃²⁺] chemiluminescence (CL) was developed for the rapid and sensitive determination of metoclopramide hydrochloride. The method is based on the CL reaction of metoclopramide with Ru(dipy)₃²⁺ and KMnO₄ in a sulfuric acid medium. Under the optimum conditions, a calibration graph was obtained over the concentration range 0.005-3.5 μg ml⁻¹ with a limit of detection (S/N=2) of 1 ng ml⁻¹. The correlation coefficient was 0.99993 (n=8) with a relative standard deviation of 0.48% for 10 determinations of 1 μg ml⁻¹ of drug. The method was successfully applied to the determination of metoclopramide in pharmaceutical preparations and biological fluids after IP administration of 25 mg kg⁻¹ dose to rats. The elimination half-life was 2.5±0.4 h.     

Solid-state pH nanoelectrode based on polyaniline thin film electrodeposited onto ion-beam etched carbon fiber

An ultramicro pH sensor has been constructed based on a thin polyaniline film that was electrochemically deposited onto a carbon fiber nanometer-size electrode. The substrate nanoelectrodes were fabricated using ion-beam conically etched carbon fibers with tip diameters ranging ca. from 100 to 500 nm. The polyaniline film was deposited from HCl solution containing the aniline monomer by cycling the potential between −0.2 and +1.0 V. The electromotive force (emf) signal between the pH sensitive polyaniline-coated nanoelectrode and an Ag/AgCl reference electrode was linear over the pH range of 2.0-12.5 with a slightly super-Nernstian slope of ca. −60 mV/pH unit. Response times ranged from several sec at pHs around 7 up to 2 min at pH 12.5. The proposed pH nanoelectrode displayed high ion selectivity with respect to K⁺, Na⁺, Ca²⁺, and Li⁺, with log K_H,M values around −12 and has a working lifetime of about 20 days. Key parameters important for the pH nanoelectrode performance, including polyaniline film preparation, selectivity, response time, temperature dependence, relative coating thickness, stability, and reproducibility, have been characterized and optimized. The performance of the pH nanoelectrode was examined by measuring the pH of several real samples including body fluids (serum, urine) and low ionic strength water samples (rain, deionized and tap water). The results agreed very well with those obtained by using commercial glass pH electrodes. The proposed pH nanoelectrode demonstrated attractive properties and seems particularly promising for use under physiological conditions.     

Evaluation of the parameters of the Bender equation of state for low acentric factor fluids and carbon dioxide

Volumetric properties of several low acentric factor fluids (Ar, CH₄, C₂H₆, Kr, N₂, Ne, O₂, Xe) as well as CO₂ are modeled using the Bender equation of state. This equation is a linear function of 19 adjustable parameters, which are evaluated from properties data, using a linear numerical procedure. The validity of the EOS is tested by calculating the Joule-Thomson inversion curve. A simple model is in particular used to correlate the inversion properties predicted by the Bender equation, expressed in term of reduced pressure as a function of reduced temperatures ranging from 0.8 to 6. The simple correlation reproduces accurately the used data. We employ data on state behaviour ρ(P,T) of homogeneous fluid phases, vapour-liquid equilibrium, second virial coefficient and the coordinates of the critical point.     

Supercritical Propanol-Water Synthesis and Comprehensive Size Characterisation of Highly Crystalline anatase TiO2 Nanoparticles

Highly crystalline anatase TiO₂ nanoparticles have been synthesised in less than 1 min in a supercritical propanol-water mixture using a continuous flow reactor. The synthesis parameter space (T, P, concentration) has been explored and the average particle size can be accurately controlled within 10-18 nm with narrow size distributions (2-3 nm). At subcritical conditions amorphous products are obtained, whereas a broad range of T and P in the supercritical regime gives 11-14 nm particles. At high temperature and pressure, the particles size increase to 18 nm. The nanoparticles have been extensively characterised with powder X-ray diffraction (PXRD), transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) with excellent agreement on size and size distribution parameters. The SAXS analysis suggests disk-shaped particles with diameters that are approximately double the height. For comparison, a series of conventional autoclave sol-gel syntheses have been carried out. These also produce phase-pure anatase nanoparticles, but with much broader size distributions and at much longer synthesis times (hours). The study demonstrates that synthesis in supercritical fluids is a very promising method for manipulating the size and size distribution of nanoparticles, thus removing one of the key limitations in many applications of nanomaterials.     

Multi‐stage high order semi‐Lagrangian schemes for incompressible flows in Cartesian geometries

Efficient transport algorithms are essential to the numerical resolution of incompressible fluid‐flow problems. Semi‐Lagrangian methods are widely used in grid based methods to achieve this aim. The accuracy of the interpolation strategy then determines the properties of the scheme. We introduce a simple multi‐stage procedure, which can easily be used to increase the order of accuracy of a code based on multilinear interpolations. This approach is an extension of a corrective algorithm introduced by Dupont & Liu (2003, 2007). This multi‐stage procedure can be easily implemented in existing parallel codes using a domain decomposition strategy, as the communication pattern is identical to that of the multilinear scheme. We show how a combination of a forward and backward error correction can provide a third‐order accurate scheme, thus significantly reducing diffusive effects while retaining a non‐dispersive leading error term. Copyright © 2016 John Wiley & Sons, Ltd.     

Determination of hydroxysafflor yellow A in biological fluids of patients with traumatic brain injury by UPLC‐ESI‐MS/MS after injection of Xuebijing

A simple, novel, specific, rapid and reproducible ultra‐performance liquid chromatography electrospray ionization tandem mass spectrometry method has been developed and validated for the determination of hydroxysafflor yellow A (HSYA) in biological fluids (plasma, urine and cerebrospinal fluid) of patients with traumatic brain injury after intravenous injection of Xuebijing (XBJ). Liquid–liquid extraction was performed, and separation was carried out on an Acquity UPLC? BEH C₁₈ column, with gradient elution using a mobile phase composed of methanol and 0.1% formic acid at a flow rate of 0.3 mL/min. A triple quadrupole tandem mass spectrometer with electrospray ionization was used for the detection of HSYA. The mass transition followed was m/z 611.0 → 491. The retention time was less than 3.0 min. The calibration curve was linear in the concentration range from 2 to 6125 ng/mL for cerebrospinal fluid, plasma and urine. The intra‐ and inter‐day precisions were <10%, and the relative standard deviation of recovery was <15% for HSYA in biological matrices. The method was successfully applied for the first time to quantify HSYA in the biological fluids (especially in cerebrospinal fluid) of patients with traumatic brain injury following intravenous administration of XBJ. Copyright © 2014 John Wiley & Sons, Ltd.     

Identification,quantification and Chrastil modelling of wheat straw wax extraction using supercritical carbon dioxide

Supercritical carbon dioxide (scCO₂) can be used as a “green” selective solvent for extractions of wheat straw waxes. For the first time, the crude extraction yields of wheat straw waxes and the yields of a single high value group of components (wax esters) using various scCO₂ conditions (305.15 to 373.15 K and 7.5 to 40 MPa) have been modelled using the Chrastil equation (Chrastil, 1982). The model accurately predicts both the crude yield and percentage of valuable wax esters within the extracts enabling maximum extraction efficiency. The key compounds within the waxes (fatty acids, sterols, fatty alcohols, wax esters, β-diketones and alkanes) have been identified and quantified. This study highlighted that, 14,16 hentriacontanedione was extracted at critical temperature and pressure in concentrations of 1000 μg.g⁻¹ straw. This molecule could demonstrate significant potential as a natural chelate for metal recovery and also in the formation of super-hydrophobic coatings.     

Water waves trapped by thin submerged cylinders in a two‐layer fluid: Discrete eigenvalue

Exact solutions of the linear water‐wave problem describing oblique water waves trapped by a submerged horizontal cylinder of small (but otherwise fairly arbitrary) cross‐section in a two‐layer fluid are constructed in the form of convergent series in powers of the small parameter characterising the “thinness” of the cylinder. The terms of this series are expressed through the solutions of the exterior Neumann problem for the Laplace equation describing the flow of unbounded fluid past the cylinder.