Reversed-phase liquid chromatography without organic solvent for determination of tricyclic antidepressants

The chromatographic behavior of seven tricyclic antidepressants (amitryptiline, clomipramine, doxepin, imipramine, maprotiline, nortryptiline, and trimipramine) was examined with micellar mobile phases containing the nonionic surfactant Brij-35. Acetonitrile-water mixtures were also used for comparison purposes. Tricyclic antidepressants are moderately polar basic drugs, which are positively charged in the usual working pH. This gives rise to a strong association with the alkyl chains and residual ionized silanols in silica-based stationary phases, which is translated in a high consumption of organic solvent to get appropriate retention times. Brij-35 modifies the surface of the stationary …

Estimation of Solute-Stationary Phase and Solute-Mobile Phase Interactions in the Presence of Ionic Liquids

The presence of free silanols on alkyl-bonded reversed-phase stationary phases is responsible for broad and asymmetrical peaks when basic drugs are chromatographed with conventional octadecylsilane (C18) columns due to ionic interactions. In the last few years, ionic liquids (ILs) have attracted attention to reduce this undesirable silanol activity. ILs should be considered as dual modifiers (with a cationic and anionic character), which means that both cations and anions are able to adsorb on the stationary phase, creating a positively or negatively charged layer, depending on the relative adsorption. The accessibility of basic compounds to the silanols is prevented by both the IL cation a…

Analytical Techniques for Furosemide Determination

Abstract Due to the clinical importance of furosemide, a large number of analytical procedures to detect the presence of this drug in pharmaceutical and physiological samples has been developed. In this manuscript, a review of the most frequent analytical techniques described to determine furosemide is presented. Special attention has been paid to spectrophotometric and chromatographic techniques, but also to relevant methods using capillary electrophoresis or flow‐injection analysis, as well as the detection modes coupled to these techniques. The review also focuses on the different degradation pathways of the drug and cautions to prevent it, otherwise rarely or confusedly mentioned in the…

On the use of ionic liquids as mobile phase additives in high-performance liquid chromatography. A review.

The popularity of ionic liquids (ILs) has grown during the last decades in several analytical separation techniques. Consequently, the number of reports devoted to the applications of ILs is still increasing. This review is focused on the use of ILs (mainly imidazolium-based associated to chloride and tetrafluoroborate) as mobile phase additives in high-performance liquid chromatography (HPLC). In this approach, ILs just function as salts, but keep several kinds of intermolecular interactions, which are useful for chromatographic separations. Both cation and anion can be adsorbed on the stationary phase, creating a bilayer. This gives rise to hydrophobic, electrostatic and other specific in…

Ionic Liquid Based Headspace Solid-Phase Microextraction-Gas Chromatography for the Determination of Volatile Polar Organic Compounds

Solid-phase microextraction (SPME) with an ionic liquid (IL) coating was developed for headspace extraction of a group of low molecular weight alcohols (ethanol, n-propanol, butanol, and isopropyl alcohol), acetone, ethyl acetate, and acetonitrile. A first SPME fiber was simply coated with a dedicated IL whose synthesis is described. A second SPME fiber was prepared by gluing silica (Si) particles on which the synthesized IL was chemically bonded. The analytes SPME extraction was optimized for time, temperature, and NaCl salting out content. The headspace extracted analytes were determined by simple temperature desorption into the hot injection port of a gas chromatograph. The coated-IL fib…

Comparison of surfactant-mediated liquid chromatographic modes with sodium dodecyl sulphate for the analysis of basic drugs

In reversed-phase liquid chromatography (RPLC), basic drugs are positively charged at the usual working pH range and interact with free anionic silanols present in conventional silica-based stationary phases. This translates into stronger retention and tailed and broadened peaks. This problem can be resolved by the addition of reagents to the mobile phase that are adsorbed on the stationary phase, avoiding the access of solutes to silanols. Among these additives, surfactants under micellar conditions have provided good silanol suppressing potency through the technique known as micellar liquid chromatography (MLC). The most common example of this is anionic sodium dodecyl sulphate (SDS). Whe…

Micellar Liquid Chromatography: Fundamentals

The reversed phase liquid chromatography (RPLC) mode with surfactant above the critical micellar concentration (CMC) has been called micellar liquid chromatography (MLC). In pure micellar systems, the retention behavior is explained by considering three phases or environments: surfactant-modified stationary phase, bulk aqueous solvent, and micellar pseudo-phase. Surfactant adsorption on the porous RPLC packing affects chromatographic retention, owing to the change of diverse surface properties of the stationary phase. In pure micellar systems, the retention behavior is explained by considering three phases or environments: surfactant-modified stationary phase, bulk aqueous solvent, and mice…

Micellar Liquid Chromatography: Method Development and Applications

High Submicellar Liquid Chromatography

Surfactant addition above the critical micellar concentration (CMC), in reversed-phase liquid chromatography (RPLC), was proposed as a way to modify the selectivity and analysis time, giving rise to a chromatographic mode called micellar liquid chromatography (MLC). However, solutions containing only surfactant are too weak and yield poor peak shape. This was remediated by the addition of a small amount of organic solvent. To preserve the existence of micelles, in MLC high contents of organic solvent are avoided. Nevertheless, there is no reason to neglect the potentiality of mobile phases containing a surfactant above its CMC in water and a high organic solvent content (without micelles). …

Oil-In-Water Microemulsion Liquid Chromatography

Oil-in-water microemulsions (O/W MEs) are obtained spontaneously by mixing two immiscible liquids (water and oil) in the presence of a surfactant. A co-surfactant is also often needed for ME stabil...

Micellar liquid chromatography in doping control.

The issue of doping control in sport involves the development of reliable analytical procedures and efficient strategies to process a large number of samples in a short period of time. Reversed-phase LC techniques with aqueous–organic mobile phases and MS or diode-array detection yield satisfactory results for the identification of prohibited substances in sport. However, time-consuming sample pretreatment steps are required, which reduces sample throughput. Micellar LC (MLC) that uses hybrid mobile phases of surfactant above its critical micellar concentration and organic solvent has been revealed as an interesting alternative. The surfactant sodium dodecyl sulfate solubilizes the protein…

Micellar liquid chromatography: suitable technique for screening analysis.

The screening capability of micellar liquid chromatography (MLC) is discussed using the reported chromatographic data of several sets of compounds (amino acids, beta-blockers, diuretics, phenethylamines, phenols, polynuclear aromatic hydrocarbons, steroids and sulfonamides) and new results (sulfonamides and steroids). The chromatographic data are treated with an interpretive optimisation resolution procedure to obtain the best separation conditions. Usually, the pH and the concentration of surfactant (sodium dodecyl sulfate, SDS, or cetyltrimethylammonium bromide) for the optimal mobile phase were 2.5-3 and0.12 M, respectively. The nature and concentration of organic solvent depended on the…

Identification of Leguminosae gums and evaluation of carob-guar mixtures by capillary zone electrophoresis of protein extracts.

A procedure for the extraction and capillary zone electrophoresis (CZE) separation of proteins from carob, guar and tara gums in a background electrolyte (BGE) of pH 9 containing 0.1% polyvinyl alcohol is described. The CZE protein profiles exhibit characteristic peaks for each one of the Leguminosae gums, which can be used to construct models capable of identifying samples of carob, guar and tara gums, and predicting the guar content in binary carob-guar mixtures of different geographical origin and harvested in different years. The classification and prediction models are constructed by using linear discriminant analysis (LDA) and multiple linear regression (MLR), respectively. An excelle…

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…

Effect of ionization and the nature of the mobile phase in quantitative structure-retention relationship studies.

Abstract The octanol–water distribution constant, commonly called partition coefficient, Po/w, is a parameter often retained as a measure of the hydrophobicity of a molecule. log Po/w, for a given molecule, can be conveniently evaluated constructing correlation lines between standard retention factor logarithms (log k) in reversed-phase liquid chromatography (RPLC) and standard log Po/w values. Many compounds of pharmaceutical interest can be quite hydrophobic and have, simultaneously, basic nitrogen atoms or acidic sulfur containing groups in their structure. This renders them ionizable. The hydrophobicity of the molecular drug form (Po/w value) is completely different from its ionic form …

New Insights and Recent Developments in Micellar Liquid Chromatography

Abstract: Micellar liquid chromatography (MLC) is an efficient alternative to conventional reversed–phase liquid chromatography with hydro‐organic mobile phases. Almost three decades of experience have resulted in an increasing production of analytical applications. Current concern about the environment also reveals MLC as an interesting technique for “green” chemistry because it uses mobile phases containing 90% or more water. These micellar mobile phases have a low toxicity and are not producing hazardous wastes. After a rapid overview of the two first decades of the technique, this review focuses on the recent advances on fundamental aspects and analytical applications. Traditional and n…

Extraction of β-blockers from urine with a polymeric monolith modified with 1-allyl-3-methylimidazolium chloride in spin column format

Abstract A glycidyl methacrylate-based monolith was modified with imidazolium-based ionic liquid (IL) to be used as stationary phase for solid-phase extraction (SPE). The host monolithic support was prepared by in-situ UV polymerization in spin column format. Two approaches were developed to incorporate the IL into the polymeric monolithic matrix: generation of IL onto the surface monolith, and copolymerization by addition of the IL to the polymerization mixture, which gave the best results. The resulting sorbent materials were morphologically characterized and used for the isolation of five β-blockers from human urine samples. All SPE steps were accomplished by centrifugation, which reduce…

Interpretive optimisation of organic solvent content and flow-rate in the separation of β-blockers with a Chromolith RP-18e column

The chromatographic performance of a Chromolith RP-18e column was comprehensively examined for a group of basic drugs (beta-blockers), eluted with isocratic ACN-water mixtures at increasing flow-rate up to 6 mL/min. As the flow-rate increases at fixed mobile phase composition, peak distribution (selectivity) is maintained, but the relative peak widths increase. This reduces the resolution below satisfactory values for closely eluting compounds. With the monolithic column, flow-rate becomes thus an important factor to be optimised, in addition to the mobile phase composition. Since, theoretically, retention factors (k) are independent of the flow-rate, the classical quadratic model relating …

Correction of the deviations in the retention times with Chromolith columns associated to the flow rate: Implications in the modelling of the retention behaviour

In a previous work (J. Sep. Sci. 2009, 32, 2793-2803), we reported an interpretive optimisation approach to achieve maximal resolution in minimal analysis time, based on models describing the retention and peak shape as a function of mobile phase composition and flow rate. The method was applied to the separation of a group of basic drugs in a Chromolith column. In that work, we found that the retention factors were sensitive to the flow rate. The reason of the observed deviations in retention times is the increase in the column volume at the applied pressure, which decreases the linear velocity inside the column. This behaviour forced to include a correction term in the model that describe…