Francesco Saliu

HPLC–APCI-MS analysis of triacylglycerols (TAGs) in historical pharmaceutical ointments from the eighteenth century

AbstractThe lipid fractions of residues from historical pharmaceutical ointments were analysed by reversed-phase liquid chromatography coupled with atmospheric pressure chemical ionization and mass spectrometer detection. The residues were contained in a series of historical apothecary jars, dating from the eighteenth century and conserved at the “Aboca Museum” in Sansepolcro (Arezzo, Italy) and at the pharmacy of the “Real Cartuja de Valldemossa” in Palma de Majorca (Spain). The analytical protocol was set up using a comparative study based on the evaluation of triacylglycerol (TAG) compositions in raw natural lipid materials and in laboratory-reproduced ointments. These ointments were prepared following pharmaceutical recipes reported in historical treatises and used as reference materials. The reference materials were also subjected to stress treatments in order to evaluate the modification occurring in the TAG profiles as an effect of ageing. TAGs were successfully detected in the reproduced formulations even in mixtures of up to ten ingredients and after harsh degradative treatments, and also in real historical samples. No particular interferences were detected from other non-lipid ingredients of the formulations. The TAG compositions detected in the historical ointments indicated a predominant use of olive oil and pig adipose material as lipid ingredients. The detection of a high level of tristearine and myristyl-palmitoyl-stearyl glycerol in two of the samples suggested the presence of a fatty material of a different origin (maybe a ruminant). On the basis of the positional isomer ratio, sn-PPO/sn-POP, it was possible to hypothesize an exclusive use of pig fat in one sample. We also evaluated the application of principal component analysis of TAG profiles as an approach for the multivariate statistical comparison of the reference and historical ointments. FigureHPLC-APCI-MS analysis of triacylglycerols (TAGs) in historical pharmaceutical ointments from the eighteenth century

Identification of triacylglycerols in archaelogical organic residues by core-shell reversed phase liquid chromatography coupled to electrospray ionization-quadrupole-time of flight mass spectrometry.

A method based on the use of a Poroshell 120 EC-C18 column (3.0mm×50mm, 2.7μm) with a high resolution electrospray ionization-quadrupole-time of flight (ESI-Q-ToF) tandem mass spectrometer as detection system was optimized for the identification of triacylglycerols (TAGs) in complex archaeological residues. The best performances in chromatographic separation and Q-ToF detection sensitivity were reached by using a mixture of iPrOH/MeOH at a 0.6mL/min flow rate. Triolein (OOO) was eluted in 12.30min and the chromatographic resolution against tripalmitin (PPP) was 1.4. Very good limits of detection and quantification limits were also achieved (LOD<0.03μg/g LOQ<0.10μg/g). These achievements were compared with the results provided by traditional particle columns and with the results reported in the recent literature regarding TAGs analysis in archaeological residues. Thanks to the unprecedented chromatographic separation and detection sensitivity attained, it was possible for the first time to perform TAGs researches in archaeological residues and reference materials with a dataset containing more than 500 molecular formula.

Sphingoid esters from the molecular distillation of squid oil: A preliminary bioactivity determination.

A mixture of sphingoid esters was isolated (1.4% w/w) from the molecular distillation of crude squid visceral oil. A preliminary investigation on the bioactivity profile and toxic potential of this residue was carried out by in vitro experiments. No cytotoxicity and a moderate lipase inhibition activity were highlighted.

The Synthesis of Phthalic Anhydride via Ozonation of Naphthalene

The oxidation of naphthalene (1) (Scheme 1) in dichloromethane or acetonitrile with excess ozone gives phthalic aldehyde (3), 2-formyl benzoic acid (4) and phthalic anhydride (8). Small amounts of the (E)- and (Z)-isomer of 3-phenyl-(2-formyl)-propenal (10) and (11) are also observed in some cases. The reaction is faster in acetonitrile than in dichloromethane owing to the higher solubility of ozone in the former solvent. The reaction is faster on lowering the temperature because of the increase of the concentration of ozone in solution at lower temperature. With a 1:1 or a 1:2 naphthalene:ozone ratio high conversion and low selectivity for the anhydride (8) is observed.

Podophyllotoxin and Antitumor Synthetic Aryltetralines. Toward a Biomimetic Preparation

Organic compounds obtained from radical coupling of phenylpropenoidic phenols have an important biological role. In fact, they constitute organic polymers such as lignin (Higuchi,1985) lignans (Ayers & Loike, 1990), suberin (Berdards et al. 1995) and algal cell walls (Ragan, 1984). To date, several hundreds of these lignans have been isolated. Whilst their biological role in plants is unclear and remains to be fully elucidated, they have been shown to display a substantial range of biological activity and have a long and fascinating medical history that emanates from their use as folk remedies to treat an assortment of conditions (Bett, 1951). They are typically dimers and their primary physiological role in plants is in plant defense (Beutner & Ferenczy, 1997). Some lignans have found application in medicine, such as podophyllotoxin in venereal wart treatment (Meresse et al, 2004), or its semisynthetic derivatives etoposide, and teniposide in cancer therapies (Ward, 1997).

Application of a 1,1,3,3-tetramethylguanidine (TMG)/MeOH-CO2 in situ derivatization procedure for the gas chromatographic characterization of the fatty acid profile in olive oil.

Abstract1,1,3,3-Tetramethylguanidine (TMG), methanol and carbon dioxide were investigated as switchable polarity solvents (SPS) in the simultaneous derivatization and extraction of triacylglycerols for the gas chromatographic (GC) characterization of olive oil. Three commercial olive oils were used as test samples. Results of the developed method did not differ statistically from those provided by reference derivatization procedures. The transesterification reaction was carried out under a very mild condition, one step and in situ, and no particular matrix interferences were evidenced. The method represented the first example of the use of a switchable polarity mixture for the preparation of methyl ester derivatives of fatty acids (FAME).

Stereoselective Addition of Grignard Reagents and Lithium Alkyls onto 3,5-Disubstituted-1,3-oxazolidine-2,4-diones

Abstract 3-Benzyl-5-methyl-1,3-oxazolidine-3,4-diones react with Grignard reactants and with lithium alkyls to yield 4-substituted 3-benzyl-4-hydroxy-5-methyl-1,3-oxazolidine-2-ones. The reaction is stereoselective and follows Crams rule. GRAPHICAL ABSTRACT

N-Aryl Lactams by Regioselective Ozonation of N-Aryl Cyclic Amines

Ozonation of N-aryl-cyclic amines in organic solvents gave N-aryl-lactams regioselectively. In particular, 4-(4-aminophenyl)-morpolin-3-one, a key intermediate in the preparation of factor Xa inhibitors, was obtained in fair yields. The method represents an alternative approach for the lactamization of tertiary N-arylic substrates and is based on a “metal-free” introduction of the carbonyl function into the heterocyclic ring.

Microplastic and charred microplastic in the Faafu Atoll, Maldives

Microplastics are recognized as a growing threat for the marine environment that may even affect areas generally considered pristine. In this work we surveyed the microplastic contamination in the Faafu Atoll (Maldives, Indian Ocean) across twelve sampling station, located either inside or outside the reef rim. Sediments and seawater samples were collected. Despite the remoteness of the atoll, the scarce local population and low touristic annual afflux, the detected average abundance were 0.32 ± 0.15 particles/m3 in the surface water and 22.8 ± 10.5 particles/m2 in the beach sediments. Polymers identified through Fourier-Transform Infrared spectroscopy were mostly polyethylene, polypropylene, polystyrene, polyvinylchloride, polyethyleneterephtalate, and polyamide. Elastomeric residues and charred microparticles were also found. In particular, the charred microparticles were prevalently located nearby the inhabited island and they might be considered a peculiarity of the area, related to local practice of burning plastic waste at the shoreline.

Lipid classes and fatty acids composition of the roe of wild Silurus glanis from subalpine freshwater.

The fat content and the fatty acid composition of the roe of European catfish (Silurus glanis) wild specimens captured in the Lambro river basin (Como, Northern Italy) were investigated in order to assess their nutritional value. Total extracted lipid values on roe weight were 5.8-6.3%. Phospholipids (40.2-43.6%) and triacylglycerols (31.8-34.7%) were the most represented lipid classes. Relevant amount of cholesteryl esters (14.3-15.6%) were also detected. The main fatty acids were palmitic, oleic and cis-4,7,10,13,16,19-docosahexaenoic acid (DHA). Total saturated fatty acids were 28.1-30.9%, monounsaturated fatty acids were 28.2-30.6%, and polyunsaturated fatty acids (PUFAs) were 26.7-29.1%. The good found content of phospholipids and ω3-polyunsaturated fatty acids encourage further investigation for the exploitation of Silurus glanis roe in food products and/or supplements.