Temperature Responsive × Fast Chiral Comprehensive Liquid Chromatography: a New 2D-LC Platform for Resolving Mixtures of Chiral Isomers.

Chiral resolution of solutes occurring in mixtures of unrelated species is of relevance in life sciences and in pharmaceutical analysis. While this is conceptually achievable by comprehensive two-dimensional liquid chromatography (LC × LC), few approaches exist whereby the second dimension comprises the chiral separation. The latter is preferable in combination with a conventional reversed phase type of separation in the first dimension as it offers an extension of a conventional achiral analysis. The implementation of such rapid chiral analyses in the second dimension was, thus far, limited by the challenging transfer of the first dimension mobile phase to the second dimension while still achieving chiral separation. In this study, the combination of temperature-responsive and reversed-phase chiral liquid chromatography is assessed in terms of enantioselective separation of a broad range of pharmaceutical compounds. Applying temperature-responsive liquid chromatography (TRLC) in the first dimension allows for analyses to be performed under purely aqueous conditions, which then allows for complete and more generic refocusing of (organic) solutes prior to the second dimension. This offers an enhanced ability to employ fast and broad compositional gradients over the chiral dimension, which broadens the applicability of the technique. In the proposed platform, seven chiral columns (superficially porous and fully porous columns (comprising both polysaccharide and macrocyclic antibiotic phases)) and four mobile phase gradients were screened on a pharmaceutical test mixture. The platform was shown to be able to offer the necessary resolving power for the molecules at hand and offers a new approach for chiral screening of mixtures of unrelated compounds.

Selective extraction and determination of Cr(VI) in food samples based on tandem electromembrane extraction followed by electrothermal atomic absorption spectrometry.

In this study, electromembrane extraction (EME) combined with micro-EME (µ-EME) was used for the selective extraction of Cr(VI) from food samples (milk powder, Ocimum basilicum, and fish samples). Electrothermal atomic absorption spectrometry was used for the quantification of Cr(VI). Under the optimized extraction conditions, the extraction recovery of Cr(VI) was 73.7%. This proposed method provided a linear range from 0.01 to 5.0 ng/mL and the limit of detection (LOD) and limit of quantification (LOQ) were 0.003 and 0.010 ng/mL. The %RSD (n = 5) was in the range of 11.2-11.8% at 0.05, 1.0 and 2.5 ng/mL of Cr(VI), and the enrichment factor was 584. The accuracy of the method was evaluated by analysis of SRM 2700 as a certified reference material (CRM) and result was in good agreement with the certified value.

Combination of electromembrane extraction and electro-assisted liquid-liquid microextraction: A tandem sample preparation method.

As a well-known extraction procedure, electromembrane extraction (EME) was combined with electro-assisted liquid-liquid microextraction (EA-LLME) in the present work, which resulted in a promising method. This hyphenated sample preparation method, named EME-EA-LLME, was followed by GC for the determination of two model analytes (clomipramine and imipramine). The effective parameters of both EME and EA-LLME (such as organic solvent, pH of acceptor and sample solutions, voltage and extraction time) were optimized. The proposed EME-EA-LLME procedure demonstrated good linearity with coefficients of determination, R2 ≥ 0.998 over the concentration range of 0.5-750 ng/mL. Limit of detection for both analytes was 0.15 ng/mL. The corresponding repeatability ranged from 6.9 to 12.2% (n = 3). The high enrichment factors were obtained as 770.3 and 561.4 for imipramine and clomipramine, respectively. The advantages of this tandem sample preparation method were low detection limits, simplicity, low cost, and short analysis time (<10 min). Finally, the optimized method was used to extract and determine the analytes in urine and wastewater samples. Overall, the results revealed that the developed EME-EA-LLME procedure had better extraction efficiency in comparison with EME and EA-LLME alone.

Study on electrical current variations in electromembrane extraction process: Relation between extraction recovery and magnitude of electrical current.

This contribution presents an experimental approach to improve analytical performance of electromembrane extraction (EME) procedure, which is based on the scrutiny of current pattern under different extraction conditions such as using different organic solvents as supported liquid membrane, electrical potentials, pH values of donor and acceptor phases, variable extraction times, temperatures, stirring rates, different hollow fiber lengths and the addition of salts or organic solvents to the sample matrix. In this study, four basic drugs with different polarities were extracted under different conditions with the corresponding electrical current patterns compared against extraction recoveries. The extraction process was demonstrated in terms of EME-HPLC analyses of selected basic drugs. Comparing the obtained extraction recoveries with the electrical current patterns, most cases exhibited minimum recovery and repeatability at the highest investigated magnitude of electrical current. . It was further found that identical current patterns are associated with repeated extraction efficiencies. In other words, the pattern should be repeated for a successful extraction. The results showed completely different electrical currents under different extraction conditions, so that all variable parameters have contributions into the electrical current pattern. Finally, the current patterns of extractions from wastewater, plasma and urine samples were demonstrated. The results indicated an increase in the electrical current when extracting from complex matrices; this was seen to decrease the extraction efficiency.