Liquid-Liquid Flow in a Capillary Microreactor: Hydrodynamic Flow Patterns and Extraction Performance

The capillary micro reactor, with four stable operating flow patterns and a throughput range from grams per hour to kilograms per hour, presents an attractive alternative to chip-based and microstructured reactors for laboratory- and pilot-scale applications. In this article, results for the extraction of 2-butanol from toluene under different flow patterns in a water/toluene flow in long capillary microreactors are presented. The effects of the capillary length (0.4-2.2 m), flow rate (0.1-12 mL/min), and aqueous-to-organic volumetric flow ratio (0.25-9) on the slug, bubbly, parallel, and annular flow hydrodynamics were investigated. Weber-number-dependent flow maps were composed for capillary lengths of 0.4 and 2 m that were used to interpret the flow pattern formation in terms of surface tension and inertia forces. When the capillary length was decreased from 2 to 0.4 m, a transition from annular to parallel flow was observed. The capillary length had little influence on slug and bubbly flows. The flow patterns were evaluated in terms of stability, surface-to-volume ratio, throughput, and extraction efficiency. Slug and bubbly flow operations yielded 100% thermodynamic extraction efficiency, and increasing the aqueous-to-organic volumetric ratio to 9 allowed for 99% 2-butanol extraction. The parallel and annular flow operating windows were limited by the capillary length, thus yielding maximum 2-butanol extractions of 30% and 47% for parallel and annular flows, respectively.

Determination of the Tolman length in the improved Derjaguin-Broekhoff-de Boer theory for capillary condensation of ethanol in mesoporous thin films by ellipsometric porosimetry

Ethanol adsorption-desorption isotherms on well-organized mesoporous silica and titania films with hexagonal pores structure were studied by ellipsometric porosimetry. The mesopore volume Was calculated from the change of the effective refractive index at the end points of the isotherm. An improved Derjaguin-Broekhoff-de Boer (IDBdB) model for cylindrical pores is proposed for the determination of the pore size. In this model, the disjoining pressure isotherms were obtained by measuring the thickness of the ethanol film on a non-porous film with the same chemical composition. This approach eliminates uncertainties related to the application of the statistical film thickness determined via t-plots in previous versions of the DBdB model. The deviation in the surface tension of ethanol in the mesopores from that of a flat interface was described by the Tolman parameter in the Gibbs-Tolman-Koening-Buff equation. A positive value of the Tolman parameter of 0.2 nm was found from the fitting of the desorption branch of the isotherms to the experimental data obtained by Low Angle X-ray Diffraction (LA-XRD) and Transmission Electron Microscopy (TEM) measurements in the range of pore diameters between 2.1 and 8.3 nm. (C) 2009 Elsevier Inc. All rights reserved.

Surveillance study of a number of synthetic and natural growth promoters in bovine muscle samples using liquid chromatography-tandem mass spectrometry

A simple, new method permitting the simultaneous determination and confirmation of trace residues of 24 different growth promoters and metabolites using liquid chromatography-mass spectrometry was developed and validated. The compounds were extracted from bovine tissue using acetonitrile; sodium sulphate was also added at this stage to aid with purification. The resulting mixture was then evaporated to approximately 1 ml and subsequently centrifuged at high speed and an aliquot injected onto the LC-MS/MS system. The calculated CC values ranged between 0.11 and 0.46 mu g kg-1; calculated CC were in the range 0.19-0.79 mu g kg-1. Accuracy, measurement of uncertainty, repeatability and linearity were also determined for each analyte. The analytical method was applied to a number of bovine tissue samples imported into Ireland from third countries. Levels of progesterone were found in a number of samples at concentrations ranging between 0.28 and 30.30 mu g kg-1. Levels of alpha- and beta-testosterone were also found in a number of samples at concentrations ranging between 0.22 and 8.63 mu g kg-1 and between 0.16 and 2.08 mu g kg-1 respectively.

Screening and Quantitative Confirmatory Method for the Analysis of Glucocorticoids in Bovine Milk Using Liquid Chromatography-Tandem Mass Spectrometry

An LC/MS/MS method was developed and validated for the simultaneous identification, confirmation, and quantification of 12 glucocorticoids in bovine milk. The method was validated in accordance with the criteria defined in Commission Decision 2002/657/EC. The developed method can detect and confirm the presence of dexamethasone, betamethasone, prednisolone, flumethasone, 6 alpha-methylprednisolone, fluorometholone, triamcinolone acetonide, prednisone, cortisone, hydrocortisone, clobetasol propionate, and clobetasol butyrate in bovine milk. Milk samples are extracted with acetonitrile; sodium chloride is subsequently added to aid partition of the milk and acetonitrile mixture. The acetonitrile extract is then subjected to liquid-liquid purification by the addition of hexane. The purified extract is evaporated to dryness and reconstituted in a water acetonitrile mixture, and determination is carried out by LC/MS/MS. The method permits analysis of up to 30 samples in 1 day.

Development of a rapid, multi-class method for the confirmatory analysis of anti-inflammatory drugs in bovine milk using liquid chromatography tandem mass spectrometry

A rapid liquid chromatography tandem mass spectrometry (LC-MS/MS) method has been developed and validated for the simultaneous identification, confirmation and quantitation of seven licensed anti-inflammatory drugs (AIDS) in bovine milk. The method was validated in accordance with the criteria defined in Commission Decision 2002/657/EC. Two classes of AIDS were investigated, corticosteroids and non-steroidal anti-inflammatory drugs (NSAIDs). The developed method is capable of detecting and confirming dexamethasone (DXM), betamethasone (BTM), prednisolone (FRED), tolfenamic acid (TV), 5-hydroxy flunixin (5-OH-FLU). meloxicam (MLX) and 4-methyl amino antipyrine (4-MAA) at their associated maximum residue limits (MRLs). These compounds represent all the corticosteroids and NSAIDs licensed for use in bovine animals producing milk for human consumption. These compounds have never been analysed before in the same method and also 4-methyl amino antipyrine has never been analysed with the other licensed NSAIDs. The method can be considered rapid as permits the analysis of up to 30 samples in one day. Milk samples are extracted with acetonitrile; sodium chloride is added to aid partition of the milk and acetonitrile mixture. The acetonitrile extract is then subjected to liquid-liquid purification by the addition of hexane. The purified extract is finally evaporated to dryness and reconstituted in a water/acetonitrile mixture and determination is carried out by LC-MS/MS. Decision limit (CC alpha) values and detection capability (CC beta) values have been established for each compound. (C) 2009 Elsevier B.V. All rights reserved.

Confirmatory method for the determination of various acetylgestagens in animal kidney fat using liquid chromatography-tandem mass spectrometry

A confirmatory method has been developed and validated that allows for the simultaneous detection of medroxyprogesterone acetate (MPA), megestrol acetate (MGA), melengestrol acetate (MLA), chlormadinone acetate (CMA) and delmadinone acetate (DMA) in animal kidney fat using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The compounds were extracted from kidney fat using acetonitrile, defatted using a hexane wash and subsequent saponification. Extracts were then purified on Isolute CN solid-phase extraction cartridges and analysed by LC-MS/MS. The method was validated in animal kidney fat in accordance with the criteria defined in Commission Decision 2002/657/EC. The decision limit (CC) was calculated to be 0.12, 0.48, 0.40, 0.63 and 0.54 g kg-1, respectively, for MPA, MGA, MLA, DMA and CMA, with respective detection capability (CC) values of 0.20, 0.81, 0.68, 1.07 and 0.92 g kg-1. The measurement uncertainty of the method was estimated at 16, 16, 19, 27 and 26% for MPA, MGA, MLA, DMA and CMA, respectively. Fortifying kidney fat samples (n = 18) in three separate assays showed the accuracy of the method to be between 98 and 100%. The precision of the method, expressed as % RSD, for within-laboratory reproducibility at three levels of fortification (1, 1.5 and 2 g kg-1 for MPA, 5, 7.5 and 10 g kg-1 for MGA, MLA, DMA and CMA) was less than 5% for all analytes.

Determination of thyreostat residues from bovine matrices using high-performance liquid chromatography

High-performance liquid chromatography (HPLC) methodologies were evaluated for the detection and quantification of thyreostatic drug residues in cattle serum and thyroid tissue. The paper details a protocol, using a simple ethyl acetate extraction for the determination of thiouracil, tapazole, methyl thiouracil, propyl thiouracil and phenyl thiouracil in thyroid tissue. Using two sequential HPLC injections, and quantitative analysis, in two steps, all five thyreostats were detectable at concentrations greater than 2.45-4.52 ng/g. Modifications to a published method for detection of thyreostatic residues in serum involving the addition of mercaptoethanol and a freezing step are described. The modifications improved sensitivity and allowed detection of the five thyreostats at levels greater than 16.98-35.25 ng/ml. Young bulls were treated with thyreostats to demonstrate the validity of the methodologies described. Administered thyreostats were not absorbed equally by the test animals and the compounds were not all detected in the serum samples removed at 7 days following drug withdrawal. These experiments indicate the necessity to be able to detect thyreostat residues in a variety of matrices. (C) 1998 Elsevier Science B.V. All rights reserved.

LIQUID-CHROMATOGRAPHY THERMOSPRAY MASS-SPECTROMETRIC ASSAY FOR TRENBOLONE IN BOVINE BILE AND FECES

A liquid chromatography-thermospray mass spectrometric assay was developed and validated to confirm the presence of illegal residues of the synthetic androgenic growth promoter, trenbolone acetate, in cattle. The assay was specific for 17alpha-trenbolone, the major bovine metabolite of trenbolone acetate. Methods were developed for the determination of 17alpha-trenbolone in both bile and faeces, the most appropriate matrices for the control of trenbolone acetate abuse. The clean-up.procedure developed relied on enzymatic hydrolysis, followed by sequential liquid-liquid and liquid-solid extraction. The extracts were then subjected to immunoaffinity chromatography. 17alpha-Trenbolone was detected by selected ion monitoring at m/z 271 using positive ion thermospray ionisation. The limit of detection was approximately 0.5 ng/g in faeces and 0.5 ng/ml in bile.

DETECTION OF CLENBUTEROL RESIDUES IN BOVINE LIVER, MUSCLE, RETINA AND URINE USING GAS-CHROMATOGRAPHY MASS-SPECTROMETRY

A gas chromatographic/mass spectrometric method is described for the detection of clenbuterol residues in liver, muscle, urine and retina. Tissue samples are first digested using protease and any clenbuterol present is extracted using a simple liquid/liquid extraction procedure. The dried extracts are then derivatized using methylboronic acid and the derivatives are subjected to gas chromatography/mass spectrometry on a magnetic sector instrument. The detection limit of the assay is 0.05 ng g-1 clenbuterol in liver, muscle or urine using a 10 g sample size, and 4 ng g-1 in retina using a 0.5 g sample size. The assay is made very specific by using selected ion monitoring of three ions at a resolution of 3500 and by ion ratio measurements. The precision and reproducibility of the assay are enhanced by the use of a deuterated internal standard, with a typical coefficient of variation of 3%.