Lipid profile of fish species by liquid chromatography coupled to mass spectrometry and a novel linear retention index database

In a previous article, Rigano et al. established a new linear retention index system for the identification of triacylglycerols by liquid chromatography methods only on the basis of the retention behavior and independently from many experimental parameters. In that work, a database of 209 compounds was built, but only 54 of them, typical of vegetable oils, were confirmed by mass spectrometry. The aim of the present research is to extend the applicability of the novel approach to more complex samples, such as fish lipid extracts, and assess the complementarity between mass spectromtery and retention information to achieve univocal identification. With this purpose, a new software was implemented to make the identification process easy and automatic as in gas chromatography‐mass spectrometry where the retention index filter is added in the spectral search to discriminate between compounds with similar mass spectrometry spectra. A total of 69 species were identified and, thanks to their baseline separation obtained by an ultra high performance liquid chromatography method, a semiquantification was also performed. The species under investigation were Dicentrarchus labrax, coming from aquaculture and the wild. Some differences in their native lipid composition were observed, probably related to a different diet. A major number of samples would be necessary to confirm such a preliminary finding.     

Carbon–Carbon Bond Forming and Cleavage in the Reactions of Isopropenyl-acetylene and 2-Methyl-hex-1-en-3-yne with Fe3(CO)12 in Basic Methanolic Solution. The X-ray Structure of Fe2(CO)5[μ-η7-{RCC(H)C(CH3)CR}] (R=CH3(=CH2))

The title complex is the main product of the reaction of Fe₃(CO)₁₂ with isopropenylacetylene in basic methanolic solution (followed by acidification); it is obtained upon carbon–carbon bond forming and dimerization of the alkyne. The same complex is also obtained by reacting Fe₃(CO)₁₂ in CH₃OH/KOH solution with 2-methyl-hex-1-en-3-yne; carbon–carbon bond cleavage presumably occurs to form isopropenylacetylene, which then reacts with the iron carbonyl. The unprecedented structure of the complex has been determined with a X-ray diffraction analysis.

A straightforward synthetic access to symmetrical glycosyl disulfides and biological evaluation thereof

Symmetrical glycosyl disulfides can be prepared within a few hours from per-O-acetylated precursors via a sequential approach entailing short reactions and no purification of any intermediate. The final thiolate-to-disulfide oxidation step is noticeably accelerated by low amounts of phenyl diselenide under air. Applicability of the strategy to non-saccharidic symmetrical alkyl disulfides has also been examined. A preliminary assay of the cytotoxic activity of symmetrical 1,1'- disulfides was performed on two human tumor cell lines, and a noteworthy activity was recorded for a range of these synthetic compounds.     

Nitroimidazole and glucosamine conjugated heteroscorpionate ligands and related copper(II) complexes. Syntheses, biological activity and XAS studies

New nitroimidazole and glucosamine conjugated heteroscorpionate ligands, namely 2,2-bis(3,5-dimethyl-1H-pyrazol-1-yl)-N-(2-(2-methyl-5-nitro-1H-imidazol-1-yl)ethyl)acetamide (L(MN)) and 1,3,4,6-tetra-O-acetyl-2-{[bis(3,5-dimethyl-1H-pyrazol-1-yl)acetyl]amino}-2-deoxy-β-D-glucopyranose (L(DAC)), respectively, were synthesized by direct coupling of preformed side chain acid and amine components. The related copper(II) complexes {[(L(MN))(2)Cu]Cl(2)}, and {[(L(DAC))(2)Cu]Cl(2)} have been prepared from the reaction of CuCl(2)*2H(2)O with L(MN) or L(DAC) ligand in methanol solution. Single crystal structural characterization was undertaken for the L(MN) ligand. In the absence of a coordinated metal core, the overall arrangement of the ligand is determined by some loose intra- and inter-molecular nonbonding contacts. X-Ray Absorption Spectroscopy (XAS) has been used to probe the local structure of the two copper(II) complexes, {[(L(MN))(2)Cu]Cl(2)} and {[(L(DAC))(2)Cu]Cl(2)}. The EXAFS analysis has permitted the identification of the local environment of the copper site. Copper interacts with 2 units of ligand in both complexes, and it is found to be 6-fold coordinated. Its local structure is described by four Cu-N and two Cu-O interactions to form a pseudo-octahedron core, with a 0.14 ? lengthening of the Cu-O bond length in the case of L(DAC) complex with respect to the L(MN) one, likely due to the higher steric hindrance of the glucosamine moiety. The XANES analysis agrees with these results, also confirming the Cu(II) formal copper oxidation state for both complexes. The new copper(II) complexes {[(L(MN))(2)Cu]Cl(2)} and {[(L(DAC))(2)Cu]Cl(2)} as well as the corresponding uncoordinated ligands were evaluated for their cytotoxic activity towards a panel of several human tumour cell lines. The results reported here indicate that both copper(II) complexes show similar spectra of cytotoxicity and very low resistance factors (RF < 2) against C13* ovarian cancer cells which have acquired resistance to cisplatin.     

Molecules and heterostructures at TiO2 surface: the cases of H2O,CO2, and organic and inorganic sensitizers

Research on Chemical Intermediates - TiO2-based (nano)materials are widely exploited in systems and devices of actual technological interest, because of their outstanding physical and chemical...     

Recent Advances in the Synthesis of Inorganic Materials Using Environmentally Friendly Media

Deep Eutectic Solvents have gained a lot of attention in the last few years because of their vast applicability in a large number of technological processes, the simplicity of their preparation and their high biocompatibility and harmlessness. One of the fields where DES prove to be particularly valuable is the synthesis and modification of inorganic materials—in particular, nanoparticles. In this field, the inherent structural inhomogeneity of DES results in a marked templating effect, which has led to an increasing number of studies focusing on exploiting these new reaction media to prepare nanomaterials. This review aims to provide a summary of the numerous and most recent achievements made in this area, reporting several examples of the newest mixtures obtained by mixing molecules originating from natural feedstocks, as well as linking them to the more consolidated methods that use “classical” DES, such as reline.     

Analysis of corticosteroids by high performance liquid chromatography-electrospray mass spectrometry

A high performance liquid chromatography electrospray mass spectrometry (HPLC-ESI-MS) method, for the detection of corticosteroids in cosmetics has been developed. A water-acetonitrile linear gradient on a C-18 reversed-phase column was found to be suitable in separating triamcinolone and its main derivatives, which greatly differ in lipophilicity. Detection was performed in negative electrospray ionisation mode. Good correlation between peaks areas and solutions concentration was found in the range 0.05-10.0 micro g ml(-1) and the detection limits resulted in the range of 20-45 pg injected. The method was successfully applied to the analysis of real samples of shampoo.     

Electrodeposited glucose oxidase/anionic clay for glucose biosensors design

An amperometric glucose biosensor was developed using an anionic clay matrix (layered double hydroxide (LDH), Ni/Al-NO₃) for the immobilization of glucose oxidase (GOx). The biofilm was prepared by electrodeposition of the clay and GOx and subsequent cross-linking with glutaraldeyde. The Pt surface modified with the Ni/Al-NO₃ shows a much reduced noise, giving rise to a better signal to noise ratio for the currents relative to H₂O₂ oxidation, and a linear range for H₂O₂ determination wider than the one observed for bare Pt electrodes. Under the optimised operative conditions, the performances of the biosensor have been evaluated by measuring the steady-state currents (at +0.45 V versus SCE) to increasing concentrations of glucose in “air saturated” 0.1 M phosphate buffer (pH 7.0). Both batch and flow injection modes were explored. The response to glucose was linear up to 8.0 and 12.0 mM, and the sensitivities were 7.7 ± 0.1 and 19.1 ± 0.2 mA M⁻¹ cm⁻², respectively. The current response of the biosensors does not significantly change for 15 consecutive days in batch and for 10 days in flow, at least, if stored at 4 °C in phosphate buffer, when not in use. The effects of interferants and applicability to fruit juices and soft drinks analysis of the biosensor were also investigated.     

Granular species segregation under vertical tapping: effects of size, density, friction, and shaking amplitude

We present extensive molecular dynamics simulations on species segregation in a granular mixture subject to vertical taps. We discuss how grain properties, e.g., size, density, friction, as well as shaking properties, e.g., amplitude and frequency, affect such a phenomenon. Both the Brazil nut effect (larger particles on the top, BN) and the reverse Brazil nut effect (larger particles on the bottom, RBN) are found and we derive the system comprehensive "segregation diagram" and the BN to RBN crossover line. We also discuss the role of friction and show that particles which differ only for their frictional properties segregate in states depending on the tapping acceleration and frequency.     

Intercalation of iron(III) hexacyano complex in a Ni,Al hydrotalcite-like compound

The product obtained by the intercalation of hexacyanoferrate(III) inside a Ni, Al hydrotalcite-like compound (Htlc) has been characterized using XRD, FT-IR, Raman, and XAS spectroscopy. The intercalation was carried out by anionic exchange of the originally existing chloride ions. The combined use of those techniques gave more insight on the insertion chemistry of Htlcs. Extended X-ray absorption fine structure spectra of the intercalated Htlc demonstrated that the native structure was stable during the iron complex insertion, whereas the exchange process occurred with a partial reduction of hexacyanoferrate(III). Both Raman and FT-IR spectroscopy pointed out the concomitant formation of K(2)NiFe(II)(CN)(6) and KNiFe(III)(CN)(6). The effect of aging on the intercalated product is also addressed.