Effect of chemically bonded stationary phases and mobile phase composition on beta-blockers retention in RP-HPLC

The effects of stationary and mobile phase on retention of 18 beta-adrenolytic drugs (beta-blockers) have been studied. Four 'deactivated surface' stationary phases (polar-embedded or end-capped) were examined. Special attention was drawn to the cholesterolic (SG-CHOL) and alkylamide (SG-AP) stationary phases, and their application for analysis of the compounds. The retention of analyzed substances was also examined in terms of mobile phase composition. Sixteen different configurations of mobile phases were prepared, all based on methanol and acetonitrile with ammonium acetate and ammonium formate. The difference in retention between ammonium formate and acetate water solutions, and peak shape changes related to the addition of triethylamine (TEA), were investigated. Principal component analysis was used to find the similarities between stationary phases. Polar-embedded phases synthesized on the same sorbent possess very similar properties. All phases based on silica gel compared with the monolithic column also showed similarities in retention of beta-blockers. The addition of TEA to the mobile phase did not influence strongly the retention, and analysis of asymmetry factors showed only a little peak broadening for a few compounds on the monolithic column.     

Porous structure of natural and modified clinoptilolites

The evaluation of the pore-size distribution (PSD) of natural and modified mesoporous zeolites, i.e., clinoptilolites is presented. We demonstrate the SEM results showing that the pores of fracture-type from 25-50 nm to 100 nm in size between clinoptilolite grains, as well as pores between crystal aggregates up to 500 nm in size are present in the studied material. The detailed distribution of pore sizes and tortuosity factor of the above-mentioned materials are determined from the adsorption-desorption isotherms of nitrogen measured volumetrically at 77 K. To obtain the reliable pore size distribution (PSD) of the above-mentioned materials both adsorption and desorption branches of the experimental hysteresis loop are described simultaneously by recently developed corrugated pore structure model (CPSM) of Androutsopoulos and Salmas. Evaluated pore size distributions are characterized by well-defined smooth peaks placed in the region of the mesoporosity. Moreover, the mean pore diameter calculated from the classical static measurement of nitrogen adsorption at 77 K correspond very well to the pore diameters from SEM, showing the applicability of the CPSM for characterization of the porosity of natural zeolites. We conclude that classical static adsorption measurements combined with the proper modeling of the capillary condensation/evaporation phenomena are a powerful method which can be applied for pore structure characterization of natural and modified clinoptilolites.     

Study of the selection mechanism of heavy metal (Pb2+, Cu2+, Ni2+, and Cd2+) adsorption on clinoptilolite

The study was carried out on the sorption of heavy metals (Ni2+, Cu2+, Pb2+, and Cd2+) under static conditions from single- and multicomponent aqueous solutions by raw and pretreated clinoptilolite. The sorption has an ion-exchange nature and consists of three stages, i.e., the adsorption on the surface of microcrystals, the inversion stage, and the moderate adsorption in the interior of the microcrystal. The finer clinoptilolite fractions sorb higher amounts of the metals due to relative enriching by the zeolite proper and higher cleavage. The slight difference between adsorption capacity of the clinoptilolite toward lead, copper, and cadmium from single- and multicomponent solutions may testify to individual sorption centers of the zeolite for each metal. The decrease of nickel adsorption from multicomponent solutions is probably caused by the propinquity of its sorption forms to the other metals and by competition. The maximum sorption capacity toward Cd2+ is determined as 4.22 mg/g at an initial concentration of 80 mg/L and toward Pb2+, Cu2+, and Ni2+ as 27.7, 25.76, and 13.03 mg/g at 800 mg/L. The sorption results fit well to the Langmuir and the Freundlich models. The second one is better for adsorption modeling at high metal concentrations.     

Identification of volatile lung cancer markers by gas chromatography–mass spectrometry: comparison with discrimination by canines

In this work, a chromatographic method for identification of volatile organic compounds was compared with canine recognition. Gas chromatography and mass spectrometry (GC-TOF MS) were used for determination of concentrations of trace gases present in human breath. The technique enables rapid determination of compounds in human breath, at the parts per billion level. Linear correlations were from 0.83-234.05 ppb, the limit of detection was the range 0.31-0.75 ppb, and precision, expressed as relative standard deviation (RSD), was less than 10.00 %. Moreover, trained dogs are able to discriminate breath samples of patients with diagnosed cancer. We found a positive correlation between dog indications and the ethyl acetate and 2-pentanone content of breath (r = 0.85 and r = 0.97, respectively). The methods presented for detection of lung cancer markers in exhaled air could be used as a potential non-invasive tool for screening. In addition, the canine method is relatively simple and inexpensive in comparison with chromatography.     

Application of TLC and OPLC in the Determination of Pigments from Natural Products

JPC – Journal of Planar Chromatography – Modern TLC - Planar chromatographic methods thin-layer chromatography (TLC) and over-pressure thin-layer chromatography (OPLC) have been...     

LC–MS/MS Determination of Catecholamines in Urine Using FMOC-Cl Derivatization on Solid-Phase Extraction Cartridge

A method for the determination of catecholamine derivatives in human urine is proposed that includes the derivatization of target compounds on a solid-phase extraction cartridge and determination of the analytes by a UHPLC method with tandem mass-spectrometric detection. 9-Fluorenyl-methoxycarbonyl chloride was used as the derivatization agent. The limits of detection for the analytes were 2.5 ng mL^?1 for 9-fluorenyl-methoxycarbonyl-adrenaline, 5 ng mL^?1 for 9-fluorenyl-methoxycarbonyl-octopamine, and 25 ng mL^?1 for 9-fluorenyl-methoxycarbonyl-dopamine. The proposed procedure was tested on real samples obtained from volunteers.