Enantioselective separations by capillary GC on derivatized cyclodextrins. Part 2: Determination of enantiomeric excess of some racemic 2,3-isopropylidene-1,2,3-cyclohexanetriol derivatives on permethyl α-, β-, and γ-cyclodextrins

Capillary GC on permethyl α-, β-, and γ-cyclodextrins has been applied to separate and quantify the enantiomers of some 2,3-iso-propylidene-1,2,3-cyclohexanetriol derivatives. Quantitative CGC data are compared to those obtained with chiral shift ¹H NMR.     

A novel pseudo simulated moving bed with solvent gradient for ternary separations

A novel pseudo simulated moving bed was suggested to separate a ternary mixture. A solvent gradient was created to make the solvent strength decreasing from zone II to zone III. Under suitable conditions, the least retained solute A moved forward and the most retained solute C moved backward in zones II and III whereas the medium retained solute B moved forward in zone II but backward in zone III to be trapped in the two zones consequently. Once the columns in zones II and III were saturated with solute B, the solvent dissolving the feed was introduced at the feed port to remove solute A from the raffinate-port and solute C from the extract-port. Finally, solute B was recovered from the extract port by stopping the liquid flow in zone II. This scheme was validated by the successful separation of dihydrocapsaicin from capsaicinoids.     

Use of intermittent jets to enhance flux in crossflow filtration

This paper deals with the influence of a new flow unsteadiness on the permeate fluxes in crossflow filtration. A pneumatically controlled valve generates intermittent jets from the main flow, causing the formation of large vortices moving downstream along the tubular membrane. The main results of the numerical calculation of such flows are given. The experimental study was carried out by filtering a bentonite suspension through an ultrafiltration mineral membrane. Time evolutions of flux were achieved in steady and unsteady operating conditions. Results concerning the influence and limits of the nozzle to tube diameter ratio and the jet velocities are discussed. The applicability of such an unsteady flow is examined with a view to effects on energy consumption and possible viscosity effects.     

Cation effect on anion separations by aza-crown ligands in liquid membranes

New carriers have been prepared based on the aza-18-crown-6 structure to facilitate membrane transport of ions. One of these incorporates four aza-18-crown-6 molecules bonded to a resorcinarene ring. The other, aza-18-crown-6 bonded to an undecyl chain, was studied as a monomeric analog. These carriers have been included in dichloromethane bulk liquid membranes (BLMs) to assess cation influence on competitive transport among anions (ReO₄⁻, NO₃⁻, ClO₄⁻). ReO₄⁻ was investigated as a non-radioactive analog of the pertechnetate anion, which is of interest in nuclear waste separations. The permeability values and selectivity for ReO₄⁻ and ClO₄⁻ were the greatest when neutral source and receiving phases were used with K⁺ as the co-transported cation. The carriers also showed selectivity for ReO₄⁻ and ClO₄⁻ over NO₃⁻ with K⁺ and Na⁺ as the co-transported cations using neutral and basic aqueous phase solutions. It was also found that some cations inhibit anion transport.     

Fast and simultaneous determination of phenolic compounds and caffeine in teas, mate, instant coffee, soft drink and energetic drink by high-performance liquid chromatography using a fused-core column

A fast HPLC method with diode-array absorbance detector and fluorescence detector for the analysis of 19 phenolic acids, flavan-3-ols, flavones, flavonols and caffeine in different types of samples was developed. Using a C₁₈ reverse-phase fused-core column separation of all compounds was achieved in less than 5 min with an overall sample-to-sample time of 10 min. Evaluation of chromatographic performance revealed excellent reproducibility, resolution, selectivity and peak symmetry. Limits of detection for all analyzed compounds ranged from 0.5 to 211 μg L⁻¹, while limits of quantitation ranged between 1.5 and 704 μg L⁻¹. The developed method was used for the determination of analytes present in different samples, including teas (black, white, green), mate, coffee, cola soft drink and an energetic drink. Concentration of the analyzed compounds occurring in the samples ranged from 0.4 to 314 mg L⁻¹. Caffeine was the analyte found in higher concentrations in all samples. Phytochemical profiles of the samples were consistent with those reported in the literature.     

Effect of temperature on the protonation of N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid in aqueous solutions: Potentiometric and calorimetric studies

The TALSPEAK process (Trivalent Actinide Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Komplexes) has been demonstrated in several pilot-scale operations to be effective at separating trivalent actinides (An³⁺) from trivalent lanthanides (Ln³⁺). However, fundamental studies have revealed undesired aspects of TALSPEAK, such as the significant partitioning of Na⁺, lactic acid, and water into the organic phase, thermodynamically unpredictable pH dependence, and the slow extraction kinetics. In the modified TALSPEAK process, the combination of the aqueous holdback complexant HEDTA (N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid) with the extractant HEH[EHP] (2-ethyl(hexyl) phosphonic acid mono-2-ethylhexyl ester) in the organic phase has been found to exhibit a nearly flat pH dependence between 2.5 and 4.5 and more rapid phase transfer kinetics for the heavier lanthanides. To help understand the speciation of Ln³⁺ and An³⁺ in the modified TALSPEAK, systematic studies are underway on the thermodynamics of major reactions in the HEDTA system under conditions relevant to the process (e.g., higher temperatures). Thermodynamics of the protonation and complexation of HEDTA with Ln³⁺ were studied at variable temperatures. Equilibrium constants and enthalpies were determined by a combination of techniques including potentiometry and calorimetry. This paper presents the protonation constants of HEDTA at T = (25 to 70) °C. The potentiometric titrations have demonstrated that, stepwise, the first two protonation constants decrease and the third one slightly increases with the increase of temperature. This trend is in good agreement with the enthalpy of protonation directly determined by calorimetry. The results of NMR analysis further confirm that the first two protonation reactions occur on the diamine nitrogen atoms, while the third protonation reaction occurs on the oxygen of a carboxylate group. These data, in conjunction with the thermodynamic parameters of Ln³⁺/An³⁺ complexes with HEDTA at different temperatures, will help to predict the speciation and temperature-dependent behavior of Ln³⁺/An³⁺ in the modified TALSPEAK process.     

Chiral separability of boron cluster species studied by screening approaches utilizing polysaccharide‐based chiral stationary phases

In this study, the screening steps of chiral separation strategies with polysaccharide‐based chiral stationary phases were applied on boron cluster compounds in normal‐phase liquid chromatography (NPLC) and polar organic solvents chromatography (POSC). Since the screening steps were initially developed to analyze organic compounds, their applicability for boron clusters was investigated. Overall, the screening steps in NPLC were applicable for the separation of zwitterions, while for anions mostly no elution was observed. A hypothesis for the latter behavior is precipitation of anions in the nonpolar mobile phases. Ten out of 11 compounds could be partially or baseline separated on the NPLC screening systems. In POSC, all zwitterions were separated on at least one of the screening systems, with an overall lower retention as in NPLC. Anions were detected but not separated in the majority of the experiments. Also their retention on the chiral stationary phases was very limited. This study showed that the chiral discrimination potential of chemically modified polysaccharides is meaningful for chiral separations of structurally chiral boron cluster species, but needs further systematic research, in which recognition mechanisms should be further explored. In addition, some unusual peaks also indicated that conditions with a high separation efficiency must first be searched for some of the tested systems. Copyright © 2014 John Wiley & Sons, Ltd.     

Pushing the speed limit in enantioselective supercritical fluid chromatography

Chromatographic enantioseparations on the order of a few seconds can be achieved by supercritical fluid chromatography using short columns packed with chiral stationary phases. The evolution of ‘world record’ speeds for the chromatographic separation of enantiomers has steadily dropped from an industry standard of 20–40 min just two decades ago, to a current ability to perform many enantioseparations in well under a minute. Improvements in instrument and column technologies enabled this revolution, but the ability to predict optimal separation time from an initial method development screening assay using the t_{min cc} predictor greatly simplifies the development and optimization of high‐speed chiral chromatographic separations. In this study, we illustrate how the use of this simple tool in combination with the workhorse technique of supercritical fluid chromatography on customized short chiral columns (1–2 cm length) allows us to achieve ultrafast enantioseparations of pharmaceutically relevant compounds on the 5–20 s scale, bringing the technique of high‐throughput enantiopurity analysis out of the specialist realm and into the laboratories of most researchers.     

Enantioselective comprehensive two‐dimensional gas chromatography. A route to elucidate the authenticity and origin of Rosa damascena Miller essential oils

The analysis of Bulgarian and Turkish Rosa damascena Miller essential oils was performed by flow‐modulated comprehensive two‐dimensional gas chromatography using simultaneous detection of the second column effluent by flame ionization and quadrupole mass spectrometric detection. Enantioselective separations were obtained by running the samples on 2,3‐di‐O‐ethyl‐6‐O‐tert‐butyldimethylsilyl‐β‐cyclodextrin column as the first column and on polyethylene glycol as the second column. The determination of enantiomeric or diastereomeric excess of some terpenoic solutes is a possible route for quality or authenticity control as well as for the elucidation of the country of origin.     

Density gradients in packed columns: II. Effects of density gradients on efficiency in supercritical fluid separations

To investigate how fluid compressibility affects efficiency in supercritical fluid separations, band dispersion along a packed capillary column was measured from on-column elution rate profiles obtained under solvating gas chromatography (SGC) conditions; this allowed efficiency to be determined with respect to position along the column. Theoretical efficiency was also modeled. The model indicates that the primary cause of band broadening in SGC is high mobile phase velocity near the column outlet. However, the experimental results show that significant band broadening also occurs near the column inlet in a region that corresponds to high elution rates of the analyte. On-column detection also revealed spatial focusing of the analyte as it moves down the column density gradient.