A review of developments in the methodology and application of microemulsion electrokinetic chromatography.

MEEKC is a mode of CE, which utilizes microemulsion (ME) as the BGE to achieve separation of a diverse range of analytes. MEs are composed of nanometer-sized oil droplets suspended in aqueous buffer which are stabilized by the presence of a surfactant and co-surfactant. These MEs are commonly referred to as oil-in-water MEs and their application in MEEKC has been extensively examined. This review details advances in the theory, methodology, and application of MEEKC during the period 2010-2012. Areas covered include online sample concentration, advances in chiral separations, use of coated capillaries, chemometric approaches, and the use of novel additives to the ME system. This review also provides the reader with an introduction to MEEKC and a presentation of recent applications.

Recent developments in the methodology and application of MEEKC.

MEEKC is an electrodriven separation technique that utilises the unique properties of a microemulsion (ME) as a background electrolyte to achieve separation of a diverse range of solutes. MEs are composed of nanometre-sized oil droplets suspended in aqueous buffer, which is commonly referred to as oil-in-water ME. The droplets are stabilised by the presence of both a surfactant and co-surfactant. The use of water-in-oil MEs in MEEKC has also been investigated. This review details the advances in MEEKC-based separations from the period June 2008 - June 2010. Areas covered include online sample concentration, suppressed electroosmosis MEEKC, chiral separations, MEEKC-MS, MEEKC-ICP-MS and ME structure characterisation. The review also includes a fundamental introduction to MEEKC, along with a review of recent applications.

Advances in the theory and application of MEEKC.

MEEKC is an electrodriven separation technique, which utilises the unique properties of a microemulsion (ME) as a background electrolyte to achieve separation of a diverse range of solutes. MEs are composed of nanometre-sized oil droplets suspended in aqueous buffer, which is commonly referred to as an oil-in-water ME. The droplets are stabilised by the presence of a surfactant and co-surfactant. The use of water-in-oil MEs in MEEKC has also been investigated. This review details the advances in MEEKC-based separations from the period 2008 to 2009. Areas covered include online sample concentration, suppressed electroosmosis MEEKC, chiral separation, MEEKC-MS, and structure-migration relationships. The review also includes a fundamental introduction to MEEKC, along with the presentation of recent applications.

Recent advances in the methodology, optimisation and application of MEEKC.

MEEKC is an electrodriven separation technique. Oil-in-water microemulsions (MEs) and to a lesser extent water-in-oil MEs have been used in MEEKC as BGEs to achieve separation of a diverse range of solutes. The more common (oil-in-water) MEs are composed of nanometre-sized droplets of oil suspended in an aqueous buffer. Interfacial tension between the oil and aqueous phase is reduced close to zero by the presence of a surfactant and a co-surfactant. MEEKC is capable of providing fast and efficient separations for a wide range of acidic, basic and neutral, water-soluble and -insoluble compounds. This review details the advances in MEEKC-based separations from the period 2006 to 2008. Areas covered include online sample concentration, chiral separation, suppressed electroosmosis MEEKC, MEEKC-MS, and the use of MEEKC in predicting migration behaviour and solute characteristics. A fundamental introduction to MEEKC, along with the presentation and discussion of recent applications is also included.

Capillary electrophoresis for pharmaceutical analysis.

This chapter describes the application of capillary electrophoresis (CE) to pharmaceutical analysis. The areas of pharmaceutical analysis covered are enantiomer separation, analysis of small molecules such as amino acids or drug counter-ions, pharmaceutical assay, related substances determinations, and physiochemical measurements such as log P and pKa of compounds. The different electrophoretic modes available and their advantages for pharmaceutical analysis are described. Recent applications of CE for each subject area are tabulated with electrolyte details. Information on electrolyte choice and method optimization to obtain optimal separations is included.

Optimisation and validation of a rapid and efficient microemulsion liquid chromatographic (MELC) method for the determination of paracetamol (acetaminophen) content in a suppository formulation.

A rapid and efficient oil-in-water microemulsion liquid chromatographic method has been optimised and validated for the analysis of paracetamol in a suppository formulation. Excellent linearity, accuracy, precision and assay results were obtained. Lengthy sample pre-treatment/extraction procedures were eliminated due to the solubilising power of the microemulsion and rapid analysis times were achieved. The method was optimised to achieve rapid analysis time and relatively high peak efficiencies. A standard microemulsion composition of 33 g SDS, 66 g butan-1-ol, 8 g n-octane in 1l of 0.05% TFA modified with acetonitrile has been shown to be suitable for the rapid analysis of paracetamol in highly hydrophobic preparations under isocratic conditions. Validated assay results and overall analysis time of the optimised method was compared to British Pharmacopoeia reference methods. Sample preparation and analysis times for the MELC analysis of paracetamol in a suppository were extremely rapid compared to the reference method and similar assay results were achieved. A gradient MELC method using the same microemulsion has been optimised for the resolution of paracetamol and five of its related substances in approximately 7 min.

Recent advances in the development and application of microemulsion EKC.

Microemulsion EKC (MEEKC) is an electrodriven separation technique. Separations are typically achieved using oil-in-water microemulsions, which are composed of nanometre-sized oil droplets suspended in an aqueous buffer. The droplets are stabilised by a surfactant and a cosurfactant. The novel use of water-in-oil microemulsions has also been investigated. This review summarises the advances in the development of MEEKC separations and also the different areas of application including determination of log P values, pharmaceutical applications, chiral analysis, natural products and bioanalytical separations and the use of new methods such as multiplexed MEEKC and high speed MEEKC. Recent applications (2004-2006) are tabulated for each area with microemulsion composition details.

Capillary electrophoresis for the analysis of small-molecule pharmaceuticals.

This paper reviews the application of CE to the analysis of small-molecule pharmaceuticals. The areas of pharmaceutical analysis covered are enantiomer separation, the analysis of small molecules such as amino acids or drug counter-ions, pharmaceutical assay, determination of related substances and physicochemical measurements such as log P and pK(a) of compounds. The different electrophoretic modes available and their advantages for pharmaceutical analysis are described. Recent applications of CE for each subject area are tabulated with electrolyte details.

Optimisation and use of water-in-oil MEEKC in pharmaceutical analysis.

Water-in-oil microemulsion electrokinetic chromatography has been applied to the separation of a range of acids, bases and neutrals and is especially suitable for very water-insoluble drug compounds. A number of operating parameters were evaluated. An optimised set of operating conditions allowed separation of a range of pharmaceutical formulations containing water-insoluble compounds. A number of novel applications for W/O microemulsions were developed and ability to quantify drug contents in tablets and a cream was shown with good precision, detector linearity and accuracy. Comparison of obtained data with those determined from a HPLC method showed acceptable agreement.

Recent advances in microemulsion electrokinetic chromatography.

Microemulsion electrokinetic chromatography (MEEKC) is an electrodriven separation technique. Separations are typically achieved using oil-in-water microemulsions, which are composed of nanometre-sized droplets of oil suspended in aqueous buffer. The oil droplets are coated in surfactant molecules and the system is stabilised by the addition of a short-chain alcohol cosurfactant. The novel use of water-in-oil microemulsions for MEEKC separations has also been investigated recently. This report summarises the different microemulsion types and compositions used to-date and their applications with a focus on recent papers (2002-2004). The effects of key operating variables (pH, surfactant, cosurfactant, oil phase, buffer, additives, temperature, organic modifier) and methodology techniques are described.

Determination of folic acid in tablets by microemulsion electrokinetic chromatography.

A microemulsion electrokinetic chromatography (MEEKC) method has been developed and validated for the determination of folic acid, a water-soluble vitamin, in a commercial tablet formulation. The analysis was performed using a microemulsion containing 0.5% (w/w) ethyl acetate, 1.2% (w/w) butan-1-ol, 0.6% (w/w) sodium dodecyl sulfate, 15% (v/v) 2-propanol and 82.7% (w/w) 10 mmol L(-1) sodium tetraborate aqueous buffer at pH 9.2. Direct UV detection at 214nm led to an adequate sensitivity without interference from sample excipients. For quantitative purposes, niacin was used as internal standard. Acceptable precision (<1.2% relative standard deviation (R.S.D.)), linearity (r = 0.9992; range from 160.0 to 240.0 microg/mL), sensitivity (limit of detection (LOD) = 2.98 microg/mL; limit of quantification (LOQ) = 9.05 microg/mL) and recovery (99.8 +/- 1.8% at three concentration levels) were obtained. Based on the performance characteristics, the proposed methodology was found suitable for the determination of folic acid in tablet formulations.

Orthogonal separations of nicotine and nicotine-related alkaloids by various capillary electrophoretic modes.

The migration behaviour of nicotine and related tobacco alkaloids was investigated using three different capillary electrophoretic (CE) modes. Novel separations were achieved both using microemulsion electrokinetic chromatography (MEEKC) and nonaqueous CE (NACE). Improved resolution compared to previous studies was obtained using free-solution CE (FSCE). Each technique resulted in different, orthogonal separation selectivity. The suitability of each method for application to the analysis of nicotine lozenges is discussed. The FSCE method was applied to the analysis of nicotine lozenges due to its compatibility with an established lozenge extraction solvent. The method used gave good injection precision and linearity. Good agreement of CE and high-performance liquid chromatography (HPLC) results was obtained. The CE method is therefore considered suitable for the quantitative determination of nicotine in nicotine lozenges.

The use of novel water-in-oil microemulsions in microemulsion electrokinetic chromatography.

We describe the novel use of water-in-oil (W/O) microemulsions to achieve unique separations in microemulsion electrokinetic chromatography (MEEKC). The choice and concentration of the buffer type, surfactant and co-surfactant were all examined and optimized. Separations of a range of neutral and acidic analytes was shown to be markedly different to that obtained by (oil-in-water) O/W MEEKC. Neutral solutes are separated by virtue of their solubility (log P) values in O/W MEEKC with the more water-insoluble solutes migrating last. This separation process does not occur in W/O, as neutral solutes are not separated in order of log P.

An initial assessment of the use of gradient elution in microemulsion and micellar liquid chromatography.

Novel microemulsion and micellar HPLC separations have been achieved using gradient elution and columns packed with reverse phase material. Initial attempts at gradient microemulsion liquid chromatography proved impossible on use of a microemulsion successfully used in capillary electrophoresis. Optimisation of the microemulsion composition allowed the generation of stable microemulsions to achieve separations in HPLC. The novel use of organic-solvent micellar chromatography in gradient elution mode was shown to give efficient separations. A range of efficient separations of pharmaceuticals and related impurities were obtained. Acidic, basic, and neutral solutes were resolved covering a wide range of water solubilities and polarities. Elution times were in the order of 4-15 minutes. Separations were briefly compared to those accomplished with a micellar HPLC system. It is proposed that gradient elution in both microemulsion and micellar HPLC can be regarded as a highly successful means of achieving resolution of complex mixtures and should be considered for routine analysis and further investigation.

Background and operating parameters in microemulsion electrokinetic chromatography.

Microemulsion electrokinetic chromatography (MEEKC) is an electrodriven separation technique. Separations are generally achieved using microemulsions consisting of surfactant-coated nanometer-sized oil droplets suspended in aqueous buffer. A cosurfactant such as a short-chain alcohol is generally used to stabilize the microemulsion. This review summarizes the various microemulsion types and compositions that have been used in MEEKC. The effects of key-operating variables such as surfactant type and concentration, cosurfactant type and concentration, buffer pH and type, oil type and concentration, use of organic solvent and cyclodextrin additions, and temperature are described. Specific examples of water-in-oil microemulsions and chirally selective separations are also covered.

Microemulsion electrokinetic chromatography.

Microemulsion electrokinetic chromatography (MEEKC) is a CE technique capable of resolving complex mixtures of charged and neutral compounds covering a wide range of solubilities. It is a relatively recently developed technique and the recent increased attention has led to a number of application reports. The background to the technique and a brief overview of reported applications is provided.