Reliable identification and quantification of anabolic androgenic steroids in dietary supplements by using gas chromatography coupled to triple quadrupole mass spectrometry.

The aim of the present research was the identification and quantification of specific anabolic androgenic steroids (AASs) and other sterane structured compounds in dietary supplements (DSs). The adulteration of DSs by these compounds is of a particular concern in athletes, because it might lead to a positive doping result. The research was focused on the optimization of a highly sensitive and selective GC-based analytical strategy using triple quadrupole MS as detector. Chromatographic method and multiple reaction monitoring (MRM) transitions of 28 target compounds were optimized. Sample clean-up was carried out by using a solid phase extraction (SPE) procedure, while the derivatization of AASs was performed by using N-methyl-N-(trimethylsilyl)-trifluoroacetamide (MSTFA). The method was validated, and the following parameters were investigated: linearity range, limit of detection, accuracy, and precision expressed in terms of intra-day precision. The calibration curves were evaluated by using regression model and resulting in a good determination coefficients (R2 ≥ 0.9912). The residuals were scattered randomly around zero. The limits of detection (LODs) were lower than 7.0 ng g-1 or ng ml-1 . The accuracy assessment was evaluated in different forms of DSs characterized by high sample-to-sample variability (liquid, powder, tablet, capsule, protein, and herbal-based). Intra-day assay precision was in all cases lower than 20%. The developed analytical method was successfully applied to the analysis of 67 commercially available dietary supplements. In five cases, one or more steroid-type compounds were found in the concentration of 5 ng g-1 -100 µg g-1 , which might result adverse analytical findings in athletes.

Characterization of the pigment fraction in sweet bell peppers (Capsicum annuum L.) harvested at green and overripe yellow and red stages by offline multidimensional convergence chromatography/liquid chromatography-mass spectrometry.

Offline multidimensional supercritical fluid chromatography combined with reversed-phase liquid chromatography was employed for the carotenoid and chlorophyll characterization in different sweet bell peppers (Capsicum annuum L.) for the first time. The first dimension consisted of an Acquity HSS C18 SB (100 × 3 mm id, 1.8 µm particles) column operated with a supercritical mobile phase in an ultra-performance convergence chromatography system, whereas the second dimension was performed in reversed-phase mode with a C30 (250 × 4.6 mm id, 3.0 µm particles) stationary phase combined with photodiode array and mass spectrometry detection. This approach allowed the determination of 115 different compounds belonging to chlorophylls, free xanthophylls, free carotenes, xanthophyll monoesters, and xanthophyll diesters, and proved to be a significant improvement in the pigments determination compared to the conventional one-dimensional liquid chromatography approach so far applied to the carotenoid analysis in the studied species. Moreover, the present study also aimed to investigate and to compare the carotenoid stability and composition in overripe yellow and red bell peppers collected directly from the plant, thus also evaluating whether biochemical changes are linked to carotenoid degradation in the nonclimacteric investigated fruits, for the first time.

Chemical characterisation of old cabbage (Brassica oleracea L. var. acephala) seed oil by liquid chromatography and different spectroscopic detection systems.

We report an extensive chemical characterisation of fatty acids, triacylglycerols, tocopherols, carotenoids and polyphenols contained in the oil extracted from old cabbage (Brassica oleracea L. var. acephala) by cold-pressing of the seeds. Analyses were performed by GC-FID combined with mass spectrometry, HPLC with photodiode array, fluorescence and mass spectrometry detection. The 94% of the total fatty acids were unsaturated, rappresented by erucic acid (more than 50%) followed by linoleic, linolenic and oleic acids accounting for approximately 10% each. The most abundant triacylglycerols (>13%) were represented by erucic-gadolenic-linoleic, erucic-eruci-linoleic and erucic-erucic-oleic. Among tocopherols, γ-tocopherol accounted for over 70% of the total content. Thirteen carotenoids and 11 polyphenols were identified and measured. In particular, the total content in carotenoids was 10.9 ppm and all-E-lutein was the main component (7.7 ppm); among polyphenols, six hydroxycinnamic acids and five flavonoids, were identified by combining information from retention times, PDA and MS data.

Interactions and chemical transformations of coronene inside and outside carbon nanotubes.

By exposing flat and curved carbon surfaces to coronene, a variety of van der Waals hybrid heterostructures are prepared, including coronene encapsulated in carbon nanotubes, and coronene and dicoronylene adsorbed on nanotubes or graphite via π-π interactions. The structure of the final product is determined by the temperature of the experiment and the curvature of the carbon surface. While at temperatures below and close to the sublimation point of coronene, nanotubes with suitable diameters are filled with single coronene molecules, at higher temperatures additional dimerization and oligomerization of coronene occurs on the surface of carbon nanotubes. The fact that dicoronylene and possible higher oligomers are formed at lower temperatures than expected for vapor-phase polymerization indicates the active role of the carbon surface used primarily as template. Removal of adsorbed species from the nanotube surface is of utmost importance for reliable characterization of encapsulated molecules: it is demonstrated that the green fluorescence attributed previously to encapsulated coronene is instead caused by dicoronylene adsorbed on the surface which can be solubilized and removed using surfactants. After removing most of the adsorbed layer, a combination of Raman spectroscopy and transmission electron microscopy was employed to follow the transformation dynamics of coronene molecules inside nanotubes.