This study deals with the nonaqueous capillary electrophoretic separation of dextromethorphan and its metabolites using a methanolic background electrolyte. The optimization of separation conditions was performed in terms of the resolution of dextromethorphan and dextrorphan and the effect of separation temperature, voltage, and the characteristics of the background electrolyte were studied. Complete separation of all analytes was achieved in 40 mM ammonium acetate dissolved in methanol. Hydrodynamic injection was performed at 3 kPa for 4 s. The separation voltage was 20 kV accompanied by a low electric current. The ultraviolet detection was performed at 214 nm, the temperature of the capillary was 25°C. These conditions enabled the separation of four analytes plus the internal standard within 9 min. Further, the developed method was validated in terms of linearity, sensitivity, and repeatability. Rat liver perfusate samples were subjected to the nonaqueous capillary electrophoretic method to illustrate its applicability.

• Klíčová slova
• Dextromethorphan, Dextrorphan, Methanol, Nonaqueous media,
• MeSH
• dextromethorfan chemie   izolace a purifikace   metabolismus   MeSH
• elektroforéza kapilární MeSH
• elektrolyty chemie   MeSH
• játra chemie   metabolismus   MeSH
• krysa rodu Rattus MeSH
• methanol chemie   MeSH
• molekulární konformace MeSH
• zvířata MeSH
• Check Tag
• krysa rodu Rattus MeSH
• zvířata MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• dextromethorfan MeSH
• elektrolyty MeSH
• methanol MeSH

Racemic mixtures of six Tröger's base derivatives were separated by chiral nonaqueous capillary electrophoresis. The separation protocol was optimized first for suitable solvents. Then the applicability of various salts dissolved in organic solvents and their mixtures was evaluated. As chiral selectors β-cyclodextrin and heptakis(2,6-di-O-methyl)-β-cyclodextrin at various concentrations were used. The best enantioselectivity for the studied analytes was obtained utilizing formamide as organic nonaqueous solvent containing a mixture of sodium citrate and tris(hydroxymethyl)aminomethane acetate as electrolytes, and β-cyclodextrin as chiral additive. The experimental results demonstrated the feasibility of nonaqueous capillary electrophoresis for enantioseparation of Tröger's base derivatives. This technique represents a suitable alternative to more commonly used capillary electrophoresis in aqueous environment.

• Klíčová slova
• Tröger's base, capillary electrophoresis, enantioseparation, nonaqueous capillary electrophoresis, β-cyclodextrin,
• Publikační typ
• časopisecké články MeSH

A method for purity control of newly synthesized lactic acid-based liquid crystals has been developed. The electrokinetic chromatography proved to be suitable for the separation of these electroneutral substances from their impurities. The separations were performed in an acidic acetonitrile-based background electrolyte (BGE) with a pseudostationary phase formed by a cationic surfactant. During the optimization step, appropriate concentrations of cetyltrimethylammonium bromide, acetic acid, and water were seeked. In the optimized method, separations were carried out in acetonitrile with 1-mol/L acetic acid, 80-mmol/L cetyltrimethylammonium bromide, and 6% (v/v) water. Interesting positive effects of a small water content in the BGE on electroosmotic flow and resolution of liquid crystal substances from their impurities were observed and discussed. Samples of five liquid crystal substances, both pure and containing impurities from synthesis, were analyzed. The identification of analytes was based on a comparison of relative migration times related to the migration time of mesityl oxide. For all five samples, impurities were separated from the liquid crystals and the method thus showed its viability. To the best of our knowledge, this method is used for the first time for the purity control of newly synthesized liquid crystals. This method can be used to confirm or complement the results obtained by commonly used high-performance liquid chromatography and supercritical fluid chromatography methods. Furthermore, the electrokinetic chromatography method requires very small amounts of sample, solvents, and buffer constituents. Overall, its operational costs are significantly lower.

• Klíčová slova
• capillary electrophoresis, electrokinetic chromatography, liquid crystals, nonaqueous,
• MeSH
• acetonitrily chemie   MeSH
• cetrimonium MeSH
• chromatografie micelární elektrokinetická kapilární * metody   MeSH
• elektrolyty MeSH
• kapalné krystaly * MeSH
• superkritická fluidní chromatografie * MeSH
• voda chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• acetonitrily MeSH
• cetrimonium MeSH
• elektrolyty MeSH
• voda MeSH

We present a short review of recent computational and experimental studies on surfaces of solutions of inorganic salts in polar nonaqueous solvents. These investigations complement our knowledge of aqueous interfaces and show that liquids such as formamide, liquid ammonia, and ethylene glycol can also surface-segregate large polarizable anions like iodide, albeit less efficiently than water. For liquids whose surfaces are covered with hydrophobic groups (e.g. methanol), the surface-ion effect all but disappears. Based on the present data a general picture of inorganic-ion solvation at the solution-vapor interface of polar liquids is outlined.

• MeSH
• amoniak MeSH
• anorganické látky chemie   MeSH
• chemické jevy MeSH
• chemie fyzikální MeSH
• formamidy MeSH
• glycerol MeSH
• hydrofobní a hydrofilní interakce MeSH
• ionty chemie   MeSH
• kyselina fluorovodíková MeSH
• methanol MeSH
• rozpouštědla chemie   MeSH
• soli chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• přehledy MeSH
• Research Support, U.S. Gov't, Non-P.H.S. MeSH
• Názvy látek
• amoniak MeSH
• anorganické látky MeSH
• formamide MeSH Prohlížeč
• formamidy MeSH
• glycerol MeSH
• ionty MeSH
• kyselina fluorovodíková MeSH
• methanol MeSH
• rozpouštědla MeSH
• soli MeSH

We investigated the retention behavior of phenolic acids in nonaqueous normal-phase (NP) LC with buffered methanol/acetonitrile mobile phases on hydrosilated silica-based stationary phases. The silica hydride, Diamond hydride, Bidentate C18, and Cholesterol columns showed a higher retention of phenolic acids in the nonaqueous mobile phases than in aqueous NP mobile phases. There are some selectivity differences between the aqueous and nonaqueous mobile phases, but generally the resolution and selectivity are better in the aqueous systems. The retention of the phenolic acids tested decreased with increasing concentration of methanol in the mobile phase, up to 20% v/v methanol. At increased temperatures, the retention factors and peak widths decrease in both NP modes, showing linear ln k versus 1/T plots, due to a single retention mechanism over the temperature range from 25°C up to the column stability limit, however, the best separations are achieved at low temperatures. The enthalpic and entropic contributions to the retention were determined, and the differences between the aqueous and nonaqueous modes are possibly due to the adsorbed water layer.

• Klíčová slova
• Hydrosilated silica, Normal phase, Phenolic acids, Temperature effects,
• Publikační typ
• časopisecké články MeSH

The inclusion of electronic polarization is of crucial importance in molecular simulations of systems containing charged moieties. When neglected, as often done in force field simulations, charge-charge interactions in solution may become severely overestimated, leading to unrealistically strong bindings of ions to biomolecules. The electronic continuum correction introduces electronic polarization in a mean-field way via scaling of charges by the reciprocal of the square root of the high-frequency dielectric constant of the solvent environment. Here, we use ab initio molecular dynamics simulations to quantify the effect of electronic polarization on pairs of like-charged ions in a model nonaqueous environment where electronic polarization is the only dielectric response. Our findings confirm the conceptual validity of this approach, underlining its applicability to complex aqueous biomolecular systems. Simultaneously, the results presented here justify the potential employment of weaker charge scaling factors in force field development.

• Publikační typ
• časopisecké články MeSH

Separation of major environmental pollutants as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) by capillary electrophoresis is reported for the first time. It is not possible to resolve the solutes in an aqueous media. However, the use of methanol and acetonitrile as the background electrolyte (BGE) solvents allowed their rapid separation in an uncoated capillary. A major effort was put into BGE optimization in respect to both separation efficiency and detection for further on-line preconcentration. 5 mmol.L⁻¹ naphthalene-1-sulfonic acid and 10 mmol.L⁻¹ triethylamine dissolved in ACN/MeOH (50:50 v/v) provided best separation and detection conditions. Next, the large-volume sample stacking and the field-amplified sample injection were applied and compared. Large-volume sample stacking improved limits of detection (LODs) with regard to the standard injection by 69 times for PFOA and 143 times for PFOS with LODs of 280 and 230 nmol.L⁻¹, respectively. Field-amplified sample injection improved LODs 624 times for PFOAand 806 times for PFOS with LODs 31 and 40 nmol.L⁻¹, respectively. Both preconcentration methods showed repeatabilities of migration times less than 1.2% RSD intraday and 6.6% RSD interday. The method was applied on PFOA and PFOS analysis in a sample of river water treated with solid-phase extraction, which further improved LOD toward 5.6 × 10⁻¹⁰ mol.L⁻¹ for PFOS and 6.4 × 10⁻¹⁰ mol.L⁻¹ for PFOA and allows the method to be used for river water contamination screening or decomposition studies.

• MeSH
• acetonitrily MeSH
• chemické látky znečišťující vodu izolace a purifikace   MeSH
• elektroforéza kapilární metody   MeSH
• extrakce na pevné fázi MeSH
• fluorokarbony izolace a purifikace   MeSH
• kapryláty izolace a purifikace   MeSH
• kyseliny alkansulfonové izolace a purifikace   MeSH
• limita detekce MeSH
• methanol MeSH
• řeky chemie   MeSH
• rozpouštědla MeSH
• Publikační typ
• časopisecké články MeSH
• hodnotící studie MeSH
• práce podpořená grantem MeSH
• Názvy látek
• acetonitrile MeSH Prohlížeč
• acetonitrily MeSH
• chemické látky znečišťující vodu MeSH
• fluorokarbony MeSH
• kapryláty MeSH
• kyseliny alkansulfonové MeSH
• methanol MeSH
• perfluorooctane sulfonic acid MeSH Prohlížeč
• perfluorooctanoic acid MeSH Prohlížeč
• rozpouštědla MeSH

Nonaqueous capillary electrophoresis (NACE) using methanol (MeOH) as a solvent of the BGEs and quantum mechanical density functional theory (DFT) have been applied to determine the thermodynamic acidity (ionization) constants (pKa ) of mono- and diaza[5]helicenes, mono- and diaza[6]helicenes, and their dibenzo derivatives in MeOH and water. First, the mixed acidity constants, pKa,MeOHmix${\rm{p}}K_{{\rm{a,MeOH}}}^{{\rm{mix}}}$ , of ionogenic pyridinium groups of azahelicenes and their derivatives in MeOH were obtained by nonlinear regression analysis of pH dependence of their effective electrophoretic mobilities. The effective mobilities were measured by NACE in a large series of methanolic BGEs within a wide conventional pH range (pHMeOH 1.6-12.0) and at ambient temperature (21-26°C) in a home-made CE device. Prior to mixed acidity constant calculation, the effective mobilities were corrected to reference temperature (25°C) and constant ionic strength (25 mM). Then, the mixed acidity constants were recalculated to the thermodynamic acidity constants pKa,MeOH by the Debye-Hückel theory of nonideality of electrolyte solutions. Finally, from the methanolic thermodynamic pKa,MeOH values, the aqueous thermodynamic pKa,H2O${\rm{p}}{K_{{\rm{a,}}{{\rm{H}}_{\rm{2}}}{\rm{O}}}}$ constants were estimated using the empirical relations between methanolic and aqueous acidity constants derived for structurally related pyridine derivatives. Depending on the number and position of the nitrogen atoms in their molecules, the analyzed azahelicenes were found to be weak to moderate bases with methanolic pKa,MeOH in the range 2.01-8.75 and with aqueous pKa,H2O${\rm{p}}{K_{{\rm{a,}}{{\rm{H}}_{\rm{2}}}{\rm{O}}}}$ in the range 1.67-8.28. The thermodynamic pKa,MeOH obtained by the DFT calculations were in a good agreement with those determined experimentally by NACE.

• Klíčová slova
• Acidity constant, Azahelicenes, Density functional theory, Ionic mobility, Ionization constant,
• MeSH
• elektroforéza kapilární * metody   MeSH
• koncentrace vodíkových iontů MeSH
• kyseliny * MeSH
• methanol MeSH
• osmolární koncentrace MeSH
• termodynamika MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• kyseliny * MeSH
• methanol MeSH

A mathematical model developed for aqueous solutions and adapted to methanol as solvent was applied to predict the electromigration characteristics of analytes and background electrolytes in capillary zone electrophoresis. These characteristics are the effective mobility, and the tendency of the analyte to undergo peak-broadening due to electromigration dispersion. The input parameters for calculation like limiting mobilities and dissociation constants were experimentally determined or taken from the literature. By the aid of the model, the molar response for conductivity detection was calculated as well as the transfer ratio when indirect UV detection was used. They allow depicting the electropherogram by computer simulation. An additional important program output is the prediction of the occurrence of system- or eigenpeaks that mimic peaks of analytes or electroosmotic flow markers. The measured electropherograms were in agreement with those theoretically predicted. Deviations were attributed to ion pairing in methanolic solutions, which was not implemented in the model.

• MeSH
• elektroforéza kapilární * MeSH
• kationty MeSH
• methanol MeSH
• rozpouštědla MeSH
• teoretické modely * MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• kationty MeSH
• methanol MeSH
• rozpouštědla MeSH

A completely new method for the determination of trans-anethole (TAN) based on the anodic oxidation of this flavouring substance in pure acetonitrile using differential-pulse voltammetry has been developed. A nonaqueous carbon paste electrode bulk-modified with solid sodium dodecyl sulphate of 40 % (w/w) content was chosen as optimum. To propose TAN electrode reaction mechanism, its electrochemical behaviour was investigated at glassy carbon electrode in nonaqueous media. At optimum working conditions, the current response could be calibrated within a linear range 2-200 µmolL-1 TAN, a coefficient of determination of 0.9971, a sensitivity of 0.1122µALµmol-1, and a detection limit of 0.7 µmolL-1. A satisfactory precision (relative standard deviation of 4 %) has been achieved. The validation performed by analysis of spices and sweets provided comparable results with reference reverse-phase HPLC with spectrophotometric detection, thus confirming the practical use of the developed voltammetric method in food analysis.

• Klíčová slova
• Additive analysis, Differential pulse voltammetry, Nonaqueous carbon paste electrode, Trans-Anethole,
• MeSH
• allylbenzenové deriváty * MeSH
• analýza potravin MeSH
• koření * MeSH
• uhlík chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• allylbenzenové deriváty * MeSH
• anethole MeSH Prohlížeč
• uhlík MeSH