Molecularly imprinted polymers: a new tool for separation of steroid isomers

Molecularly imprinted polymers hold great promise for the separation of chiral compounds. A non-covalent approach to the synthesis of MIPs relies on the presence of specific and non-specific interactions, which lead to the formation of a molecular imprint. The structural differences between 17-alpha-estradiol and 17-beta-estradiol are too small to permit their efficient separation on a MIP prepared with beta-estradiol as a template. Molecular modeling revealed the presence of only one hydrogen bond that differentiates the two isomers.     

Effect of stationary phase structure on retention and selectivity tuning in the high-throughput separation of tocopherol isomers by HPLC

Four stationary phases containing different groups such as: C18, C30, alkylamide, and cholesterolic, were presented for simultaneous HPLC analysis of structural isomers of tocopherol. Especially, the influence of stationary phase structure and properties on tuning of the highly selective HPLC separation of beta- and gamma-tocopherol pair demonstrating, respectively, para- and ortho- arrangement of methyl substituents on the 6-chromanol ring, has been elucidated. It was pointed out that selectivity of each stationary phase has been a result of modulation in the mass transfer and set of unspecific interactions in the tertiary system comprising analyte <==> stationary phase <==> mobile phase. Differences in observed retention and specific selectivity of tocopherols together with the stationary phase structure investigations indicated that a spatial organization changing of chemically bonded ligands as predominantly a solvation consequence. Additional molecular modeling studies preliminary explained some of these complicated supramolecular phenomena which caused that cholesterolic stationary phase offered beneficial performance in screening of tocopherols by HPLC and biomimetic studies of not completely recognized interactions of tocopherol isomers and biological membranes.     

GC/MS analysis of gaseous degradation products formed during extrusion blow molding process of PE films

Results of the investigation of volatile organic compounds emission during polyethylene extrusion are presented. Two polymers of different processing properties were tested, namely linear low density polyethylene (ExxonMobil) and high density polyethylene (Liten FB 29). Blowing film extrusion in experimental technological line using a single screw extruder as the imported element was done. VOCs were collected on sorbent tubes containing Tenax. Gas chromatography coupled with mass spectrometry (GC/MS) was applied for the identification of volatile degradation products. PE LLD material emits a significantly larger amount of hydrocarbons than PE-HD. Its emission contains mainly C18 and C20 hydrocarbons (alkanes, 1-alkenes, and α,ω-alkadienes). In case of the PE-HD polymer, lower degradation was observed and C18 and C23 hydrocarbons were emitted.     

Chromatographic and related studies of alkylamide phases

Summary A series of chemically bonded phases has been prepared with amide groups localized by means of hydrophobic ligands. The physicochemical and chromatographic properties of such phases with chain lengths ranging from C₅ to C₈ have been examined by porosimetry, elemental analysis, solid-state NMR, and liquid chromatography. Subsequently, the conformational dynamics of these phases have been investigated by analyzing the dependence of the capacity factor (k) on the reciprocal of temperature for different organic compounds. Special emphasis has been given to the reproducibility of retention data obtained before and after temperature-dependent measurements.This work was presented at the 9th International Symposium: Advances and Applications of Chromatography in Industry, Bratislava, Slovakia, August 29–September 3, 1993.     

Determination of selected β-receptor antagonists in biological samples by solid-phase extraction with cholesterolic phase and LC/MS

A new method is presented for the determination of five selected β-receptor antagonists by HPLC, which emphasizes sample preparation via retention on a new type of silica gel sorbent used for solid-phase extraction (SPE). Sorbents of this type were obtained by the chemical modification of silica gels of various porosities by cholesterol ligands. The cholesterol-based packing material was investigated by spectroscopic methods and elemental analysis. The recoveries obtained with the extraction procedure were optimum over a relatively broad sample pH range (3.08–7.50). Analytical factors such as the sample loading, the washing step and elution conditions, the concentration of β-receptor antagonists to be extracted, and the type of sorbent were found to play significant roles in the sample preparation procedure and would therefore need to be controlled to achieve optimum recoveries of the analytes. Under optimum conditions, the recoveries of nadolol, acebutolol, esmolol, oxprenolol and propranolol from spiked buffers, blood and urine were reproducible and dependent on the polarity or hydrophilicity of the compounds. The above analytes were determined by reverse-phase high-performance liquid chromatography (HPLC) with UV and ESI-ion trap mass spectrometry (MS) detection. The described method was found to be suitable for the routine measurement of compounds that are both polar and basic, and can be applied for the analysis of biological samples such as urine and blood in clinical, toxicological or forensic laboratories. The recovery measurements were performed on spiked human urine and serum, and on real samples of mouse blood serum.