Pavel Karásek

Distribution of sulfur-containing aromatics between [hmim][Tf2N] and supercritical CO2: a case study for deep desulfurization of oil refinery streams by extraction with ionic liquids

Stringent regulations of the maximum content of sulfur in transportation fuels have prompted an intense search for new processes of deep desulfurization to complement common catalytic hydrodesulfurization. One of the alternative processes under development involves extraction of sulfur-containing aromatic compounds (SAs) from diesel fuel and gasoline with ionic liquids (ILs). In these applications, recycling of ILs will be highly important, and reextraction of SAs from ILs with supercritical carbon dioxide (scCO2) appears to be a possible method to regenerate ILs. The design and feasibility assessment of supercritical reextraction requires the partition coefficients of SAs between ILs and scCO2. We used open tubular capillary-column chromatography to measure the partition coefficients of several SAs between 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([hmim][Tf2N]) and scCO2, with [hmim][Tf2N] serving as the stationary liquid and scCO2 as the mobile phase (carrier fluid). The results confirm that the partition coefficients of SAs can be tuned within wide limits (over a decadic order of magnitude) by relatively modest changes in temperature (40–80 °C) and pressure (8.7–17.6 MPa). However, even the most favourable values of the partition coefficients of SAs between [hmim][Tf2N] and scCO2 suggest that feasibility of a large-scale supercritical reextraction process is questionable at best.

Direct continuous supercritical fluid extraction as a novel method of wine analysis. Comparison with conventional indirect extraction and implications for wine variety identification.

Direct supercritical fluid extraction (SFE) of wines with carbon dioxide was compared to SFE of the sorbent used for solid-phase extraction of the same wine samples (SPE-SFE). Compared to SPE-SFE, the direct SFE results in amore specific and representative gas chromatographic fingerprint of the wine sample. The multivariate statistical processing of the direct SFE-GC data provides a clear-cut and sharp discrimination among the individual wine varieties while the discrimination based on the SPE-SFE-GC data is relatively poor. This finding reflects the adverse effects of additional analyte-sorbent interactions and sorption/desorption steps involved in SPE-SFE.

Offline combination of pressurized fluid extraction and electron paramagnetic resonance spectroscopy for antioxidant activity of grape skin extracts assessment

A comprehensive characterization of grape skin methanolic and ethanolic extracts prepared by pressurized fluid extraction (PFE) at various temperatures within 40 to 120°C from two wine grape varieties, St. Laurent and Alibernet was performed. For the first time, an offline combination of PFE and electron paramagnetic resonance (EPR) spectroscopy together with other experimental methods was employed to assess the effect of extraction conditions on numerous extract characteristics including antioxidant or radical-scavenging ability, HPLC profile of anthocyanins, total phenolic compounds content (TPC), tristimulus color values (CIE Lab), and pH values. The properties of extracts depend on the solvent used, the mass of grape skins as well as on the extraction conditions among which the temperature plays a crucial role. In spite of wide interval of extraction temperatures, all extracts still retain their antioxidant and/or radical-scavenging properties, indicating that the extracts prepared by PFE can serve as potential source of functional food supplements or color enhancers.

Near- and supercritical water as a diameter manipulation and surface roughening agent in fused silica capillaries.

The prospects of near- and supercritical water for treatment of the inner surfaces of fused silica capillaries have been tested employing an in-lab-assembled apparatus. Unlike all other agents used for the purpose, water cannot introduce any undesirable heteroatoms to the treated surface. Theoretical background for this work comes from the well-known fact that water near its critical point can solubilize silica. The results show that depending on the temperature, water flow rate, flow mode, and exposure time, high-temperature water has wide-ranging effects on both the surface roughness and the internal diameter profile along the length of the treated capillary. By judicious selection of the operating conditions, tapered capillaries of various profiles for applications in electromigration techniques can be prepared with relatively high reproducibility. The water-treated fused silica capillaries with uniform internal diameter appear to be useful for preparation of monolithic silica capillary columns.

Capillary isoelectric focusing of probiotic bacteria from cow's milk in tapered fused silica capillary with off-line matrix-assisted laser desorption/ionization time-of-flight mass spectrometry identification.

In this study, combination of capillary isoelectric focusing (CIEF) in tapered fused silica (FS) capillary with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) is presented as an efficient approach for unambiguous identification of probiotic bacteria in real sample. For this purpose, bacteria within genus Lactobacillus were selected as model bioanalytes and cows milk was selected as a biological sample. CIEF analysis of both the cultivated bacteria and the bacteria in the milk was optimized and isoelectric points characterizing the examined bacteria were subsequently determined independently of the bacterial sample origin. The use of tapered FS capillary significantly enhanced the separation capacity and efficiency of the CIEF analyses performed. In addition, the cell number injected into the tapered FS capillary was quantified and an excellent linearity of the calibration curves was achieved which enabled quantitative analysis of the bacteria by CIEF with UV detection. The minimum detectable number of bacterial cells was 2×10(6) mL(-1). Finally, cows milk spiked with the selected bacterium was analyzed by CIEF in tapered FS capillary, the focused and detected bacterial cells were collected from the capillary, deposited onto the cultivation medium, and identified using MALDI-TOF MS afterward. Our results have revealed that the proposed procedure can be advantageously used for unambiguous identification of probiotic bacteria in a real sample.

Antioxidant activity of grape skin aqueous extracts from pressurized hot water extraction combined with electron paramagnetic resonance spectroscopy.

Pressurized hot water extraction (PHWE) was employed to prepare extracts from dried grape skin of two wine grape varieties (St. Laurent and Alibernet) at various temperatures (from 40 up to 120°C) and amounts of sample (0.5, 1.0 and 1.5 g). To assess the antioxidant activity of the extracts, electron paramagnetic resonance (EPR) spectroscopy was applied involving DPPH and ABTS(+) assays. Other extract characteristics including HPLC profile of anthocyanins and total phenolic compound content were obtained as well. PHWE has also been compared with earlier results of extractions of the same grape skin samples with compressed methanol and compressed ethanol under the conditions of pressurized fluid extraction (PFE). From this comparison, PHWE emerges as the more benign and efficient extraction method to recover valuable phenolic antioxidants from grape skins for the prospective use in functional food supplements.

Silica-based monolithic capillary columns—Effect of preparation temperature on separation efficiency

The temperature effects during the sol-gel process and ageing of the silica-based monolith on the structure and separation efficiency of the capillary columns (100microm i.d., 150mm) for HPLC separations were studied. The tested columns were synthesized from a mixture of tetramethoxysilane, polyethylene glycol and urea under the acidic conditions. The temperature was varied from 40 degrees C to 44 degrees C and formation of bypass channels between the silica mold and the capillary wall was examined. The temperature of 43 degrees C was estimated as optimal for preparation of efficient silica capillary columns which were subsequently modified by octadecyldimethyl-N,N-diethylaminosilane or covered by poly(octadecyl methacrylate) and tested using standard mixture of alkylbenzenes under the isocratic conditions.

Distribution of Organic Solutes in Biphasic 1-n-Butyl-3-methylimidazolium Methyl Sulfate−Supercritical CO2 System

Interphase distribution of organic nonelectrolytes can be important in applications of biphasic solvent systems composed of a room-temperature ionic liquid and supercritical carbon dioxide (scCO(2)). Here, open tubular capillary-column supercritical fluid chromatography (SFC) with 1-n-butyl-3-methylimidazolium methyl sulfate ([bmim][MeSO(4)]) as the stationary liquid and scCO(2) as the carrier fluid was employed to measure retention factors of organic solutes within 313-353 K and 8.5-23.2 MPa. Solute selection included 18 compounds of diverse volatilities and chemical functionalities. The retention factors were converted to infinite-dilution solute partition coefficients in the biphasic [bmim][MeSO(4)]-scCO(2) system. At a constant temperature, an increase in scCO(2) density produced distinct shifts in relative retention (= separation factor), thus providing some pressure-tunable selectivity. At a particular temperature and density of CO(2), solute partition coefficients can be correlated in terms of linear solvation energy relationships. Analysis of the relative retention data by regular solution theory resulted in approximate values of the solubility parameter of CO(2)-expanded [bmim][MeSO(4)].

Isoelectric focusing in continuously tapered fused silica capillary prepared by etching with supercritical water.

This communication indicates the potential of etching with sub- and/or supercritical water for reproducible preparation of fused-silica capillaries with tapered geometry suitable for capillary isoelectric focusing (CIEF) with electroosmotic displacement. The etching procedure provided a single-piece combination of the tapered separation space with a cylindrical connection of the detection window to the electrode vial. Selected proteins and colored pI markers were used as model analytes. A comparison with conventional cylindrical capillary under comparable applied voltage and analysis time was made, and the resultant peaks were compared in terms of peak resolution under optimized conditions. In CIEF carried out in a tapered capillary with the inlet cross-section three times larger than the cross-section at the detection window, three to four times higher resolutions of corresponding peak pairs were obtained. The method described opens the way to increase the number of separable compounds without resorting to excessively high voltage.

Separation of methicillin-resistant from methicillin-susceptible Staphylococcus aureus by electrophoretic methods in fused silica capillaries etched with supercritical water.

Identification and prevention of Staphylococcus aureus-caused infections may benefit from a fast and dependable method to distinguish between the methicillin-resistant (MRSA) and methicillin-susceptible (MSSA) S. aureus strains. The current methods involving polymerase chain reaction and/or other molecular tests are usually laborious and time-consuming. We describe here a fast and low-cost method employing capillary zone electrophoresis (CZE) to distinguish between MRSA and MSSA. The method makes use of a supercritical water-treated fused silica capillary, the inner surface of which has subsequently been modified with (3-glycidyloxypropyl)trimethoxysilane. With optimized proportions of suitable additives to the background electrolyte, a CZE separation of MRSA from MSSA may be completed within 12 min. The cells were baseline-resolved, and resolution was determined to be 3.61. The isoelectric points of MSSA and MRSA were found to be the same for both groups of these strains, pI = 3.4.