Dario Giardina

Determination of ink photoinitiators in packaged beverages by gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry

A new analytical method, using gas chromatography-mass spectrometry (GC/MS) and liquid chromatography-mass spectrometry (LC/MS) techniques, was developed for the determination in packaged food beverages of five ink photoinitiator residues: 2-isopropylthioxanthone (ITX), benzophenone, 2-ethylhexyl-4-dimethylaminobenzoate (EHDAB), 1-hydroxycyclohexyl-1-phenyl ketone (IRGACURE 184) and ethyl-4-dimethylaminobenzoate (EDAB). Samples were extracted from selected beverages (milk, fruit juices and wine) and relative packagings, using n-hexane and dichloromethane, respectively, purified on solid-phase extraction (SPE) silica gel cartridges, and then analyzed in GC/MS and LC/MS. The recovery percentages, obtained spiking the beverage samples at concentrations of 4 and 10 microgl(-1) with a standard mixture of photoinitiators, were in the range 42-108% (milk), 50-84% (wine), and 48-109% (fruit juices). The repeatability of the method was assessed in all cases by the % of correlation value, that was lower than 19%. The lowest limits of detection (LODs) and limits of quantification (LOQs), obtained using GC/MS, were in the range 0.2-1 and 1-5 microgl(-1), respectively. The method was applied to the analysis of forty packaged food beverages (milk, fruit juices and wine samples). The most significant contamination was that of benzophenone, found in all samples in a concentration range of 5-217mugl(-1). Its presence was confirmed by an LC/Atmospheric-Pressure PhotoIonization (APPI)/MS/MS analysis. The photoinitiator (EHDAB) was found in eleven out of forty beverages in a concentration range of 0.13-0.8 microgl(-1). Less important was the ITX contamination, found in three out of forty samples in a range 0.2-0.24 microgl(-1). The work proposes a new method to analyze ink photoinitiator residues in polycoupled carton packaging and in contained food beverages.

Recent Advances in α1-Adrenoreceptor Antagonists as Pharmacological Tools and Therapeutic Agents

Native α1-adrenoreceptors (ARs) appear to exist as three different subtypes encoded by three genes, α1A/1a, α1B/1b, and α1D/1d. Historically, the discovery of agents selective for each of the three α1-AR subtypes has been an active area of medicinal chemistry research because of the wide number of possible therapeutic applications. Initially introduced for the management of hypertension, α1-AR antagonists have, in fact, become increasingly common in the treatment of benign prostatic hyperplasia (BPH), and are effective therapeutic tools, when characterized by an appropriate uroselective profile. The majority of these derivatives display a competitive mechanism of action and belong to a variety of structural classes, but this review is focused on compounds belonging to the quinazoline, benzodioxane, arylpiperazine, and 1,4- dihydropyridine classes.

Receptor binding profile of cyclazosin, a new α1B-adrenoceptor antagonist

Abstract The binding profile of cyclazosin, a new prazosin-related α 1 -adrenoceptor antagonist, at α 1 -, α 2 -adrenoceptors, dopamine D 2 and 5-HT 1A receptors was compared to that of 5-methylurapidil, spiperone, risperidone and other prazosin-related ligands. In addition, cyclazosin was investigated at native and cloned α 1 -adrenoceptor subtypes. Cyclazosin showed high specificity for α 1 -adrenoceptors and a 10–15-fold selectivity for α 1B ( α 1b )-adrenoceptors with respect to the α 1A ( α 1a ) subtype (p K i values of 9.23–9.57 and 8.18–8.41, respectively). However, it failed to discriminate between cloned α 1b and α 1d -adrenoceptors (p K i values of 9.23 and 9.28, respectively).

Doxazosin-related alpha1-adrenoceptor antagonists with prostate antitumor activity.

Doxazosin analogues 1-3 and 1a were synthesized and investigated at alpha1-adrenoceptors and PC-3, DU-145, and LNCaP human prostate cancer cells. Compound 1 (cyclodoxazosin) was a potent alpha(1B)-adrenoceptor antagonist displaying antiproliferative activity higher than that of doxazosin in cancer cells in vitro and in vivo, respectively. Because of its antitumor efficacy at low concentrations, lower apoptotic activity in NHDF vs tumor cells, and antiangiogenetic effect, 1 showed a better therapeutic profile relative to doxazosin.

Alkannin/shikonin mixture from roots of Onosma echioides (L.) L.: Extraction method study and quantification

This work reports the extraction procedures of alkannin/shikonin mixture from roots of six populations of Onosma echioides, by means of three extraction techniques: Soxhlet extraction, maceration and rapid solid-liquid dynamic extraction (RSLDE). Five solvents with different polarity (hexane, petroleum ether, chloroform, ethyl acetate, methanol) were also studied. Analysis of the extracts was performed by an HPLC-DAD (diode array detector) system. The most efficient extraction technique was Soxhlet procedure using ethyl acetate for 6 h. Studied samples of O. echioides showed an alkannin/shikonin content in the range of 0.02-0.24 mg/kg. Other naphthoquinone derivatives (deoxyalkannin/deoxyshikonin and 5,8-dihydroxy-2-(4-methyl-6-oxo-5,6-dihydro-2H-pyran-2-yl)-[1,4]naphthoquinone and arnebin-6) were found for the first time in O. echioides and characterized in the extracts using HPLC-MS apparatus equipped with an ESI ionization source.

Quantification of Soyasaponins I and βg in Italian Lentil Seeds by Solid Phase Extraction (SPE) and High Performance Liquid Chromatography-Mass Spectrometry (HPLC-MS)

Lentil saponins are triterpene glycosides, mainly soyasaponins I and betag (also known as VIota), with multiple health-promoting properties. This paper reports the isolation of soyasaponins I and betag from soybeans as analytical standards and the development of a new analytical procedure for quantification of their content in various cultivars of Italian lentils, by SPE-HPLC-MS. Soyasaponins I and betag were isolated from soybeans at a purity of >90% and characterized by MS/MS (ion trap) experiments. The determination of soyasaponins in lentils was performed by extraction, SPE purification, and HPLC-MS (single quadrupole) analysis; results were confirmed by MALDI-TOF experiments. Calibration curves for soyasaponin I and betag showed correlation coefficients of 0.998 and 0.997, respectively. LOD and LOQ values were 0.02 and 0.2 mg kg(-1) for soyasaponins I and 0.1 and 1 mg kg(-1) for soyasaponin betag. Recoveries calculated at a 100 mg kg(-1) fortification level ranged from 85 to 97%, with n = 10 and RSDs of <12%. In the 32 lentil samples, contents of soyasaponin I ranged from 28 to 407 mg kg(-1), whereas that of soyasaponin betag ranged from 110 to 1242 mg kg(-1).

Determination of Soyasaponins I and βg in Raw and Cooked Legumes by Solid Phase Extraction (SPE) Coupled to Liquid Chromatography (LC)–Mass Spectrometry (MS) and Assessment of Their Bioaccessibility by an in Vitro Digestion Model

Legumes contain a rich variety of phytochemicals as soyasaponins, triterpenoidal glycosides that possess multiple health-promoting properties, such as lowering of cholesterol. In this work, the quantification of soyasaponins I and βg in 60 raw and cooked legumes by using a solid phase extraction (SPE) coupled to a liquid chromatography (LC)-mass spectrometry (MS) method was carried out. Results showed that lentils are a good source of soyasaponins, with a content of soyasaponin I that ranged from 636 to 735 mg kg(-1) and of soyasaponin βg from 672 to 1807 mg kg(-1). The cooking process produced a small loss of soyasaponins in water, that is, 4.8-8.7%, and partially converted soyasaponin βg into soyasaponin I. In addition, the bioaccessibility of soyasaponins I in lentils was studied; the values ranged from 8.9 ± 0.3 to 10.6 ± 1.1% in the duodenal compartment. On the basis of these results, soyasaponins could be effective in lowering exogenous cholesterol.

Synthesis and Antimuscarinic Activity of Derivatives of 2-Substituted-1,3-Dioxolanes

Geometric cis, trans isomers, derivatives of 2-substituted-1,3-dioxolanes and 2-substituted-1,3-dioxanes were designed and studied as antimuscarinic agents. The synthesized compounds were evaluated as perchlorides and methiodides by functional tests with rabit vas deferens (putatvie M1), guinea-pig heart (M2) and guinea-pig ileum (M3). The effect of the replacement of a trimethylammonium group with a dimethylsulfonium in the two rings was also evalutated. Pharmacological results indicate that the 1,3-dioxane nucleus shows the highest stereoselective values on the studied receptors.

Levels of polychlorinated biphenyls in fish and shellfish from the Adriatic Sea

Levels of 18 polychlorinated biphenyl (PCB) congeners were determined by gas chromatography-mass spectrometry (GC-MS) in some marine species, living both in the coastal area and in deeper seawater. In some species analysis was performed separately in edible parts (fillets) and in viscera. The existence and degree of bioaccumulation was assessed studying individual species of very different size, with the smaller being younger. Furthermore, with a multivariate statistical analysis, a correlation between PCB congeners and the feeding habits and habitat of the fish was demonstrated. The results show that fat from edible parts (fish fillets) had total PCB levels in the range 22.6–601.9 µg kg−1 (with 601.9 µg kg−1 in anchovies), while fat from viscera showed much higher concentrations (407.3–916.6 µg kg−1). Bioaccumulation was confirmed, comparing PCB levels between younger and older individual hake, squid, and horned octopus. The total PCB concentration ratio (older/younger individuals) ranges from 2.11 (squid = 292.1/137.8 µg kg−1) to 3.46 (hake = 546.0/158.0 µg kg−1).

α1-Adrenoreceptor antagonists bearing a quinazoline or a benzodioxane moiety

Publisher Summary This chapter focuses on α 1 -adrenoreceptor antagonists bearing a quinazoline or a benzodioxane moiety. Prazosin, the prototype of quinazoline-bearing compounds, is a selective α 1 -adrenoreceptor antagonist widely used as a pharmacological tool for α-adrenoreceptor subtypes characterization and as an effective agent in the management of hypertension. For these reasons, prazosin represents a valid tool to explore α1-adrenoreceptor binding site topography and a lead compound in developing new therapeutically useful agents. The role of piperazine ring of prazosin has been investigated through its replacement by an α,ω-alkanediamine chain. Benzodioxanes represent one of the oldest and best known classes of α-adrenoreceptor antagonists, whose chemical structure incorporates a 1,4-benzodioxan-2-yl moiety as the main feature. WB 4101 is the prototype of α1-adrenoreceptor antagonists bearing a benzodioxane moiety. Several investigations have been devoted to improving both affinity and selectivity.