0000000000195264
AUTHOR
Josep Esteve-romero
Use of a three-factor interpretive optimisation strategy in the development of an isocratic chromatographic procedure for the screening of diuretics in urine samples using micellar mobile phases.
Screening of diuretics in urine is feasible through direct injection of the samples into the chromatographic system and isocratic reversed-phase liquid chromatography (RPLC) with micellar-organic mobile phases of sodium dodecyl sulfate (SDS) and 1-propanol. The surfactant coverage of the chromatographic column makes the addition of organic competing amines less necessary than in conventional aqueous-organic RPLC to achieve well-shaped peaks. Also, the range of elution strengths of micellar mobile phases required to elute mixtures of hydrophobic and hydrophilic diuretics is smaller. This allows the isocratic separation of the diuretics within adequate analysis times. An interpretive methodol…
Analysis of Urine Samples Containing Cardiovascular Drugs by Micellar Liquid Chromatography with Fluorimetric Detection
A simple direct injection chromatographic procedure with fluorimetric detection is successfully applied to the determination of mixtures of 4 diuretics (amiloride, bendroflumethiazide, piretanide, and triamterene) and 6 beta-blockers (acebutolol, atenolol, labetalol, metoprolol, nadolol, and propranolol), which are usually administered in combinations for the treatment of hypertension, in urine samples. The procedure makes use of C18 columns and micellar mobile phases of sodium dodecyl sulphate (SDS), propanol, and phosphate buffer at pH 3. The adequate resolution of most drugs is obtained with a chemometrics approach where the retention is modeled as a first step using the retention factor…
Micellar liquid chromatography determination of rivaroxaban in plasma and urine. Validation and theoretical aspects.
A Micellar Chromatographic method to determine rivaroxaban in plasma and urine has been developed. The samples were dissolved in the mobile phase (SDS 0.05 M – 1-propanol 12.5%, phosphate buffered at pH 7) and 20 μL directly injected, avoiding the extraction and purification steps. Using a C18 column and running under isocratic mode at 1 mL/min, analyte was eluted without interference from the matrix in <6.0 min. The detection absorbance wavelength was set to 250 nm. The procedure was validated by Food and Drug Administration guidelines in terms of: system suitability, calibration range (0.05–5 mg/L), linearity, sensitivity, robustness, carry-over effect, specificity, accuracy (−11.1 to 4.2…
Enhanced spectrophotometric determination of nicotinic acid in a sodium dodecyl sulphate micellar medium.
The spectrophotometric determination of pyridine and pyridine derivatives by means of the König reaction was studied in micellar media of sodium dodecyl sulphate (SDS), N-cetylpyridinium chloride and Triton X-100. The sensitivity was largely increased in SDS micellar medium. The attack of the pyridine ring with cyanogen bromide to produce a glutaconic aldehyde was not affected by the presence of SDS, but the yield of the coupling reaction with an arylamine to produce a polymethine dye was largely increased. In the SDS micellar medium, aniline was superior to other coupling reagents. The limits of detection (LODs) were 6 x 10(-7), 1 x 10(-6) and 5 x 10(-7)M for pyridine, pyrrol-ylmethylpyrid…
Comparison of the performance of butanol and pentanol as modifiers in the micellar chromatographic determination of some phenethylamines
Abstract A procedure was developed for the determination of several phenethylamines (amphetamine, arterenol, ephedrine, phenylephrine, phenylpropanolamine, mephentermine, methoxyphenamine, pseudoephedrine and tyramine), using micellar mobile phases of sodium dodecyl sulfate (SDS), a C18 column and UV detection. The drugs were eluted at short retention times with conventional acetonitrile–water or methanol–water mobile phases. In contrast, in the micellar system, they were strongly retained due to association with the surfactant adsorbed on the stationary phase, and needed the addition of butanol or pentanol to be eluted from the column. These modifiers allowed a simple way of controlling th…
Determination of thyreostatics in animal feed by micellar electrokinetic chromatography
The determination of the thyreostatics 2-thiouracil, its derivatives (4-methyl-2-thiouracil, 4-propyl-2-thiouracil and 4-phenyl-2-thiouracil) and methimazole in manufactured dried animal feed by micellar electrokinetic chromatography (MEKC) is described. A 99 +/- 5% extraction yield at the 20 micrograms g-1 level (n = 8) was achieved by shaking the milled fodder with methanol-1 M NaOH (80 + 20). Aliquots of the supernatant were injected in a 75 microns x 33.5 cm uncoated silica capillary using pressure; separation was performed at 23 degrees C with 15 kV (positive polarity) in a background electrolyte (BGE) containing 40 mM sodium dihydrogenphosphate, 50 mM sodium dodecyl sulfate and 15 mM …
Determination of active ingredients in cough-cold preparations by micellar liquid chromatography.
The chromatographic behaviour of some active ingredients in cough-cold pharmaceutical preparations, the antihistamine chlorpheniramine (or the dextro enantiomer dexchlorpheniramine), and the phenethylamines phenylephrine, phenylpropanolamine and pseudoephedrine, has been studied using a C(18) column, micellar mobile phases of sodium dodecyl sulphate (SDS) and pentanol, and with UV detection. All possible combinations of chlorpheniramine/phenethylamine were resolved and determined using a mobile phase of 0.15 M SDS-6% (v/v) pentanol at pH 7, with analysis time below 7 min. Repeatabilities and within laboratory precisions were evaluated at four different drug concentrations in the range 0.5-2…
Procedure for the Screening of Eggs and Egg Products to Detect Oxolonic Acid, Ciprofloxacin, Enrofloxacin, and Sarafloxacin Using Micellar Liquid Chromatography
A method based on micellar liquid chromatography was developed to determine oxolinic acid, ciprofloxacin, enrofloxacin, and sarafloxacin in eggs and egg products. The antimicrobial drugs were obtained in a micellar solution which was directly injected. The analytes were resolved using a C18 column and a mobile phase of 0.05 M sodium dodecyl sulfate—7.5% 1-propanol—0.5% triethylamine, buffered at pH 3 with phosphate salt, running under the isocratic mode. The signal was monitored by fluorescence. Validation was successfully performed according to the EU Commission Decision 2002/657/EC in terms of specificity, calibration range (LOQ to 1 mg/kg), linearity (R2 >
Chromatographic determination of diuretics in urine samples using hybrid micellar mobile phases with fluorimetric detection
Abstract A rapid and simple chromatographic procedure, that uses hybrid micellar mobile phases of sodium dodecyl sulphate (SDS), propanol and phosphate buffer at pH 3, and fluorimetric detection ( λ exc =270 nm, λ em =430 nm), is reported for the determination of mixtures of seven diuretics of diverse efficacy (amiloride, bendroflumethiazide, bumetanide, furosemide, hydroflumethiazide, piretanide and triamterene), in urine samples. The application of a sequential optimization procedure for the resolution of the mixtures of the diuretics was problematic. However, their separation was achieved through the use of an interpretive optimization procedure based on the accurate description of the r…
Sample streaks and smears in immobilized pH gradient gels
In immobilized pH gradient (IPG) gel formulations as wide as pH 4-9, encompassing neutrality and containing the pK 7.0 acrylamido buffer as one of the buffering ions, smears are directly proportional to the total amount of the pK 7.0 species. At a total level of 10 mM pK 7.0 in these gel formulations, severe smears occur not only for mildly hydrophobic proteins (e.g., recombinant alcalase and termamylase) but also for the relatively hydrophilic pI marker proteins. Streaks and smears are essentially abolished in recipes devoid of the pK 7.0 compound or in formulations containing a maximum of 3 mM of this component. Although partitioning in water/n-octanol has shown the pK 7.0 acrylamido buff…
Spectrophotometric Determination of the Antihistamines, Carbinoxamine Maleate and Doxylamine Succinate, in anN-Cetylpyridinium Chloride Micellar Medium
Abstract The pyridine antihistamines carbinoxamine maleate and doxylamine succinate were derivatized by hydrolysis with cyanogen bromide and coupling with aniline to form a polymethine dye, and determined by colorimetry. In a micellar cationic medium of N-cetylpyridinium chloride (NCPC), the reaction times were reduced and the sensitivities improved. In 0.1 M NCPC the apparent molar absorptivities of the derivatives were 5,900 and 3,500 M−1 cm−1, and the limits of detection (as 3s) were 8.6x10−7 M and 1.7x106 M, for carbinoxamine and doxylamine, respectively. The sensitivity was enhanced in a three- to six-fold factor with respect to a non-micellar medium. The reproducibility was 0.8% for 1…
Quantification of rifampicin and rifabutin in plasma of tuberculosis patients by micellar liquid chromatography
A Micellar Liquid Chromatographic method is described to determine Rifampicin and Rifabutin in plasma from Tuberculosis patients. Samples were diluted in mobile phase and then directly injected, avoiding long and tedious extraction steps. The analytes were resolved from the matrix without interferences from endogenous compounds using a mobile phase of sodium dodecyl sulfate 0.15 mol L-1–6%(v/v) 1-pentanol and phosphate buffer at pH 3, running at 1 mL min−1 through a C18 column at 25 °C. Detection was carried out by UV absorbance at 270 nm. Under these conditions, the final chromatographic analysis time was 22 min. The analytical methodology was validated following the FDA 2018 Bioanalytical…
COMPARISON OF THE COURSE SYLLABUS OF THE THEORY SUBJECT "CHEMISTRY" IN CHEMISTRY GRADE AND IN ENGINEERING STUDIES
Comunicació presentada a INTED2016, 10th International Technology, Education and Development Conference. (March 7-9, 2016, Valencia, Spain). The aim of the chemistry-related subjects, taught in the first academic year of several grades at the University Jaume I, is to provide a broad overview about general chemistry. However, these defined subjects are adapted to the structure, objectives and curricula of each grade. In this paper, a comparison of the course syllabus of the Chemistry subjects taught in the "Chemistry grade" and in several "Engineering grades" (Agricultural, Mechanical, Electrical, Industrial Technology and Chemical) is detailed. The differences and similarities of the subje…
MICELLAR LIQUID CHROMATOGRAPHIC DETERMINATION OF ANTI-CONVULSANT DRUGS IN PILLS AND CAPSULES
A simple chromatographic procedure is reported for the determination of several anti-convulsant drugs in pharmaceuticals: carbamazepine, and the benzodiazepines bentazepam, halazepam, oxazepam, pinazepam, and tetrazepam. The procedure utilizes a C18 column, a hybrid micellar mobile phase of 0.1 M SDS-3% butanol-0.1% triethylamine-0.01 M phosphate buffer (pH 3), and UV detection (230 nm). The drugs eluted in less than 13 min, in accordance to their relative polarities, as indicated by their octanol-water partition coefficients. The limits of detection (μg/mL), and intra and inter-day repeatabilities (%), for 4 μg/mL were: carbamazepine (0.03, 1.0, 4.1), bentazepam (0.05, 1.3, 1.6), halazepam…
Use of micellar mobile phases for the chromatographic determination of clorazepate, diazepam, and diltiazem in pharmaceuticals
An ODS-2 column, a micellar mobile phase of high elution strength containing 0.1M sodium dodecyl sulfate and 3% (v/v) butanol, and ultraviolet detection at 230 nm are used for the determination of either of two benzodiazepines (clorazepate and diazepam) and a benzothiazepine (diltiazem) in pharmaceuticals. The procedure is shown to be competitive against conventional chromatography with methanol-water mobile phases, especially for diltiazem. The composition of the micellar mobile phase is selected using a predictive strategy based on an accurate retention model and assisted by computer simulation. Calibration graphs are linear at least in the 2.5 to 20 microg/mL, 4 to 20 microg/mL, and 5 to…
Development of a method to determine axitinib, lapatinib and afatinib in plasma by micellar liquid chromatography and validation by the European Medicines Agency guidelines
A method based on micellar liquid chromatography to quantify the tyrosine kinase inhibitors axitinib, lapatinib and afatinib in plasma is reported. The sample pretreatment was a simple 1/5-dilution in a pure micellar solution, filtration and direct injection, without requiring extraction or purification steps. The three drugs were resolved from the matrix in 17 min, using an aqueous solution of 0.07 M sodium dodecyl sulfate – 6.0% 1-pentanol, buffered at pH 7 with 0.01 M phosphate salt as mobile phase, running under isocratic mode at 1 mL/min through a C18 column. The detection was performed by absorbance at 260 nm. An accurate mathematical relationship was established between the retention…
Use of Micellar Liquid Chromatography to Determine Mebendazole in Dairy Products and Breeding Waste from Bovine Animals
Mebendazole is an anthelmintic drug used in cattle production. However, residues may occur in produced food and in excretions, jeopardizing population health. A method based on micellar liquid chromatography (MLC) was developed to determine mebendazole in dairy products (milk, cheese, butter, and curd) and nitrogenous waste (urine and dung) from bovine animals. Sample treatment was expedited to simple dilution or solid-to-liquid extraction, followed by filtration and direct injection of the obtained solution. The analyte was resolved from matrix compounds in less than 8 min, using a C18 column and a mobile phase made up of 0.15 M sodium dodecyl sulfate (SDS)&ndash
Quantitation of antihistamines in pharmaceutical preparations by liquid chromatography with a micellar mobile phase of sodium dodecyl sulfate and pentanol
Abstract A reversed-phase liquid chromatographic procedure with a micellar mobile phase of sodium dodecyl sulfate (SDS), containing a small amount of pentanol, was developed for the control of 7 antihistamines of diverse action in pharmaceutical preparations (tablets, capsules, powders, solutions, and syrups): azatadine, carbinoxamine, cyclizine, cyproheptadine, diphenhydramine, doxylamine, and tripelennamine. The retention times of the drugs were &lt;9 min with a mobile phase of 0.15M SDS–6% (v/v) pentanol. The recoveries with respect to the declared compositions were in the range of 93–110%, and the intra- and interday repeatabilities and interday reproducibility were &lt;1.2%. Th…
CHROMATOGRAPHIC DETECTION OF SESQUITERPENE LACTONES IN PARTHENIUM PLANTS FROM NORTHWEST ARGENTINA
Several chloroformic extracts containing some sesquiterpene lactones from autochtonous plants of Parthenium hysterophorus, collected in the province of Salta (Argentina), were separated and identified by high performance reversed-phase liquid chromatography with C18 column and propanol-water mobile phases, using gradient elution and concentrations of propanol larger than 10% (v/v). Lactones previously purified and characterized by H1 RMN, C13 RMN, IR, and mass spectrometry, were used as standards. The objective of the study was to check if the nature of the lactones was modified according to the altitude of the region where the plants were grown. Among the lactones, five were already descri…
Correlation between hydrophobicity and retention data of several antihistamines in reversed-phase liquid chromatography with aqueous-organic and micellar-organic mobile phases
Abstract The correlation between the retention of 12 antihistamines (carbinoxamine, chlorpheniramine, cyclizine, cyproheptadine, dexbrompheniramine, dexchlorpheniramine, diphenhydramine, doxylamine, pheniramine, phenyltoloxamine, pyrilamine and tripelennamine), in reversed-phase liquid chromatography (RPLC) with aqueous-organic (methanol-water) and micellar-organic (sodium dodecyl sulphate (SDS)-pentanol) mobile phases of varying composition, and their octanol-water partition coefficients expressed as log P o/w (ranging between 2.02 for pheniramine and 4.92 for cyproheptadine), was examined. For this study, the retention of the drugs was measured in six mobile phases of methanol-water, and…
Determination of furosemide in urine samples by direct injection in a micellar liquid chromatographic system.
A sensitive, selective and efficient micellar liquid chromatographic (MLC) procedure was developed for the determination of furosemide (4-chloro-N-furfuryl-5-sulfamoylanthranilic acid) in urine samples by direct injection and UV detection. The procedure makes use of a C18 reversed-phase column and a micellar mobile phase of 0.05 mol l(-1) sodium dodecyl sulfate-6% v/v propanol and phosphate buffer at pH 3 to resolve furosemide from its photochemical degradation products. The importance of protecting the standards and urine samples to be analysed from light in the assay of furosemide, avoiding its degradation, was verified. The limit of quantification was 0.15 microg ml(-1) and the relative …
Determination of Pyrrole Derivatives and Hydroxyproline with 4-(Dimethylamino)benzaldehyde in a Micellar Medium
Abstract The spectrophotometric determination of pyrrole derivatives and hydroxyproline with 4-(dimethylamino)benzaldehyde (Ehrlich's reagent) in a sodium dodecyl sulphate micellar medium is studied. Pyrrole and pyrrole-2-carboxylic acid were used as model compounds for the optimization of the procedure. In the micellar medium with 0.2 M HCl at 90° C, pyrrole reacts in 15 min, whereas a HCl concentration larger than 5 M is required in the absence of the surfactant. The sensitivity increases from 1.3 to 5.6-fold with respect to the use of a non-micellar medium, for some pyrrole derivatives. The procedure is applied to the determination of hydroxyproline in meat samples.
Flow-Injection Spectrophotometric Determination of Phenolic Drugs and Carbamate Pesticides by Coupling with Diazotized 2,4,6-Trimethylaniline
Abstract A flow-injection (FI) spectrophotometric system is proposed for the determination of phenols and carbamates. In the FI manifolds, the solutions of phenols or carbamates (the latter after hydrolysis with NaOH) were injected into a diazonium ion carrier stream at pH 9.5 (buffered with tetrahydroborate), which was formed by mixing 2,4,6-trimethylaniline (TMA) with nitrate in a sodium dodecyl sulfate aqueous micellar medium. Absorbance was measured at 550 nm. The system combines the advantages derived from the use of TMA for the coupling of phenols in basic micellar media, because of the inhibition of the self-coupling reaction of the reagent, with the precision and speed of the FI pro…
Determination of isoniazid and pyridoxine in plasma sample of tuberculosis patients by micellar liquid chromatography
It is no doubt Isoniazid is a powerful tuberculosis drug, but it might give rise to Vitamin B6 (Pyridoxine) deficiency. In this case, a usual treatment is the combined administration of Isoniazid and Pyridoxine. An easy-to-conduct procedure based on Micellar Liquid Chromatography has been developed to quantify Isoniazid and Pyridoxine in plasma from Tuberculosis patients. The sample was diluted in mobile phase, filtered and directly injected, thus avoiding extraction or purification steps. Both drugs were adequately resolved from the matrix and endogenous compounds using a mobile phase made up of 0.15 M sodium dodecyl sulfate – 8%(v/v) 1-butanol – 0.01 M phosphate buffer at pH 3, running at…
Determination of albendazole and ivermectin residues in cattle and poultry-derived samples from India by micellar liquid chromatography
We have developed a method, based on micellar liquid chromatography, to determine albendazole and ivermectin in dairy products and biological waste from bovine, as well as edible tissues from poultry. Anthelmitics were resolved in less than 10 min using a C18 column and a mobile phase of 0.15 mol/L sodium dodecyl sulfate – 6% 1-pentanol at buffered at pH 7 with a 0.01 M phosphate salt, running under isocratic mode at 1 mL/min. Detection was by absorbance at 292 nm. Method was successfully validated following official validation guidelines, in terms of: selectivity, sensitivity, calibration range (0.0125−0.5 mg/kg to 25−50 mg/kg), linearity (r2 > 9990), trueness (86.3–105.6%), precision (<12…
On the Derivatization of Drugs Using 1-Nitroso-2-naphthol, 4-aminoantipyrine and 2,6-Dihaloquinone Chlorimides
Coupling of 1-nitroso-2-naphthol (1N2N), 4-aminoantipyrine (4-AAP), 2,6-dichloroquinone chlorimide (DCQC) and 2,6-dibromoquinone chlorimide (DBQC) with several bioactive substances, including adren...
Furosemide assay in pharmaceuticals by Micellar liquid chromatography: study of the stability of the drug.
A simplified high-performance liquid chromatographic procedure is described for the determination of furosemide (4-chloro-N-furfuryl-5-sulphamoylanthranillic acid), which makes use of UV detection, a C18, reversed-phase column, and micellar mobile phases of sodium dodecyl sulphate (SDS) and 1-propanol at pH 3 buffered with phosphate system. The most adequate experimental conditions to handle furosemide solutions in the analytical laboratory are studied. The mixture of furosemide and its degradation products which are formed upon light exposition was resolved with a mobile phase of 0.04 M SDS-2% propanol. Separation of furosemide from its common impurities and the hydrolytic product, 4-chlor…
Determination of sulphonamides in human urine by azo dye precolumn derivatization and micellar liquid chromatography
Abstract A high-performance liquid chromatographic method for the determination of sulphonamides in urine is reported. The drugs (sulphadiazine, sulphaguanidine, sulphamethizole, sulphamethoxazole, and sulphathiazole) were diazotized with nitrite and coupled with N-(1-naphthyl)ethylenediamine dihydrochloride in a sodium dodecyl sulphate (SDS) micellar medium. Separation of the sulphonamide azo dyes was performed on a C18 column with a 0.05 M SDS-2.4% pentanol mobile phase, which permitted the direct injection of the urine samples. The limits of detection were in the 0.1–0.3 μg/ml range.
High-performance micellar liquid chromatography determination of sulphonamides in pharmaceuticals after azodye precolumn derivatization
Abstract A chromatographic procedure with precolumn derivatization to form the N-(1-naphthyl)ethylenediamine dihydrochloride azodyes is proposed for the analysis of several sulphonamides (sodium sulphacetamide, sulphadiazine, sulphaguanidine, sulphamerazine, sulphamethizole, sulphamethoxazole, sulphanilamide and sulphathiazole) in pharmaceutical preparations (tablets, pills, capsules, suspensions and drops). The separation is performed with a 0.05 M sodium dodecyl sulphate/2.4% pentanol eluent at pH 7. The precolumn derivatization improved the resolution in the chromatograms and increased the selectivity in the determination of mixtures of sulphonamides and in preparations where other drugs…
Micellar modified spectrophotometric determination of nitrobenzenes based upon reduction with tin(II), diazotisation and coupling with the Bratton–Marshall reagent
Abstract Nitrobenzenes, such as the antibiotic chloramphenicol, the vasodilator nicardipine, and the herbicides dinitramin, dinobuton, fenitrothion, methylparathion, oxyfluorfen, parathion, pendimethalin, quintozene, and trifluralin, were determined by using a spectrophotometric method in the visible region (540 nm). The method was based on the reduction of the nitrobenzenes to arylamines with tin(II) chloride, diazotisation of the arylamines and coupling of the diazonium ions with the Bratton–Marshall reagent. The two latter reactions were performed in a micellar medium of sodium dodecyl sulphate. The linear calibration range was 2×10 −6 to 7×10 −5 M ( r >0.999), with limits of detection i…
Micellar liquid Chromatographic determination of diuretics by diazotization and coupling with the Bratton-Marshall reagent
Abstract A Chromatographic procedure that uses micellar mobile phases of sodium dodecyl sulphate (SDS) and propanol at pH 3 is reported for the determination, in urine samples, of thiazide diuretics (althiazide, bendroflumethiazide, chlorothiazide, hydrochlorothiazide, hydroflumethiazide, and trichloromethiazide), and other diuretics having a sulphonamide substituent in the benzene ring. Precolumn derivatization with sodium nitrite and N -(1-naphthyl)ethylenediamine, to form the coloured azo dyes of the hydrolyzed diuretics, decreased the polarity of the compounds and, consequently, their retention in the micellar eluents, and permitted detection in the visible region, eliminating thus the …
Chromatographic analysis of phenethylamine-antihistamine combinations using C8, C18 or cyano columns and micellar sodium dodecyl sulfate-pentanol mixtures.
The chromatographic behaviour of binary and ternary mixtures of several phenethylamines (phenylephrine, phenylpropanolamine, ephedrine, pseudoephedrine and methoxyphenamine) and antihistamines (pheniramine, carbinoxamine, doxylamine, chlorpheniramine, dexchlorpheniramine, dexbrompheniramine, diphenhydramine, tripolidine, azatadine and phenyltoloxamine), found in cough-cold pharmaceutical preparations, was studied using C8, C18 and cyano columns, micellar mobile phases of sodium dodecyl sulfate (SDS) and pentanol and UV detection. Using a C8 column and mobile phases of 0.05 mol l-1 SDS-6% v/v pentanol or 0.15 mol l-1 SDS-2% v/v pentanol at pH 7, more than 30 different phenethylamine-antihist…