[Dietary supplements on the domestic market adulterated with sildenafil and tadalafil]. / Szildenafillal és tadalafillal hamisított étrend-kiegészítok a hazai piacon.

Mandatory requirements regulating the manufacture and sale of dietary supplements are much less stringent than those related to pharmaceuticals. Hence, the sheer number and diversity of marketed products in this category has shown an unprecedented increase Europe-wide. Not surprising, that cases for incorrect marketing/promotion, incorrect recommendations for product use, as well as reported incidents of questionable product quality and/or deliberate adulterations have also become frequent in recent years. Typical adulterations consist of admixtures of synthetic pharmaceuticals to the matrix fraudulently declared to consist exclusively of extracts of various (medicinal) plants. In the present paper, the results of qualitative investigations of ten plant-based preparations, marketed in Hungary, and recommended as (or alleged to be) natural aphrodisiacs, are reported. Sildenafil and/or tadalafil or related analogs were detected in six of the ten products. These results highlight, once more, the unacceptable risks for the consumers of such adulterated dietary supplements.

Direct and indirect high-performance liquid chromatographic enantioseparation of beta-amino acids.

Direct and indirect reversed-phase (RP) high-performance liquid chromatographic methods were developed for the separation of enantiomers of 18 unnatural beta-amino acids, including several beta-3-homo amino acids. The direct separations of the underivatized analytes were performed on chiral stationary phases (CSPs) containing macrocyclic glycopeptide antibiotic teicoplanin (Chirobiotic T column) and teicoplanin aglycone (Chirobiotic TAG column). The indirect method involved pre-column derivatization with a new chiral derivatizing agent (CDA), (S)-N-(4-nitrophenoxycarbonyl)phenylalanine methoxyethyl ester ((S)-NIFE), and subsequent separation of diastereomers on Discovery C18 and Hyperpep 300 C18 columns. The different methods were compared in systematic chromatographic examinations. The effects of organic modifier, mobile phase composition, pH and flow rate on the separation were investigated.

Effects of temperature on retention of chiral compounds on a ristocetin A chiral stationary phase.

The isocratic retention of enantiomers of chiral analytes, i.e. tryptophan, 1,2,3,4-tetrahydroisoquinoline and gamma-butyrolac tone analogs, was studied on a ristocetin A chiral stationary phase at different temperatures and with different mobile phase compositions, using the reversed-phase, polar-organic and normal-phase modes. By variation of the both mobile phase composition and the temperature, baseline separations could be achieved for these enantiomers. The retention factors and selectivity factors for the enantiomers of all investigated compounds decreased with increasing temperature. The natural logarithms of the retention factors (ln k) of the investigated compounds depended linearly on the inverse of temperature (1/T). van't Hoff plots afforded thermodynamic parameters, such as the apparent change in enthalpy (deltaH(o)), the apparent change in entropy (deltaS(o)) and the apparent change in Gibbs free energy (deltaG(o) ) for the transfer of analyte from the mobile to the stationary phase. The thermodynamic parameters (deltaH(o), deltaS(o) and deltaG(o)) were calculated in order to promote an understanding of the thermodynamic driving forces for retention in this chromatographic system.

Indirect high-performance liquid chromatographic separation of stereoisomers of beta-alkyl-substituted amino acids by the application of (S)-N-(4-nitrophenoxycarbonyl)phenylalanine methoxyethyl ester as chiral derivatizing agent.

The indirect high-performance liquid chromatographic enantioresolution of beta-alkyl-substituted analogues of tyrosine, phenylalanine, 1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid and tryptophan is reported. (S)-N-(4-Nitrophenoxycarbonyl)phenylalanine methoxyethyl ester, a recently developed chiral derivatizing agent, was used for pre-column derivatization of the investigated analytes. The diastereoisomers formed were analysed under reversed-phase conditions. The effects of parameters such as the amount and type of the organic modifier and the type of the stationary phase on the resolution and retention of the derivatives were investigated. Chromatographic conditions were found for the separation of all four stereoisomers of each analyte.

Application of a new chiral derivatizing agent to the enantioseparation of secondary amino acids.

A new chiral derivatizing agent, (S)-N-(4-nitrophenoxycarbonyl)phenylalanine methoxyethyl ester, (S)-NIFE, was applied for the high-performance liquid chromatographic separation of enantiomers of 19 unnatural secondary amino acids: proline, pipecolic acid analogues, piperazine-2-carboxylic acid, morpholine-3-carboxylic acid, thiomorpholine-3-carboxylic acid and analogues containing the 1,2,3,4-tetrahydroisoquinoline, 1,2,3,4-tetrahydronorharmane, 1,2,3,4-tetrahydro-2-carboline and 2-benzazepine skeletons. Excellent resolutions were achieved for most of the investigated compounds by using a reversed-phase mobile phase system. The conditions of separation were optimized by variation of the mobile phase composition.