Structural Evidence for Pnictogen-Centered Lewis Acidity in Cationic Platinum-Stibine Complexes Featuring Pendent Amino or Ammonium Groups

As part of our continuing interest in the chemistry of cationic antimony Lewis acids as ligands for late transition metals, we have now investigated the synthesis of platinum complexes featuring a triarylstibine ligand substituted by an o-[(dimethylamino)methyl]phenyl group referred to as Ar^N. More specifically, we describe the synthesis of the amino stibine ligand Ph₂SbAr^N (L) and its platinum dichloride complex [LPtCl]Cl which exists as a chloride salt and which shows weak coordination of the amino group to the antimony center. We also report the conversion of [LPtCl]Cl into a tricationic complex [LHPt(SMe₂)]³⁺ which has been isolated as a tris-triflate salt after reaction of [LPtCl]Cl with SMe₂, HOTf and AgOTf. Finally, we show that [LHPt(SMe₂)][OTf]₃ acts as a catalyst for the cyclization of 2-allyl-2-(2-propynyl)malonate.     

1H-NMR Profiling Shows as Specific Constituents Strongly Affect the International EVOO Blends Characteristics: The Case of the Italian Oil

Considering the growing number of extra virgin olive oil (EVOO) producers in the world, knowing the influence of olive oils with different geographical origins on the characteristics of the final blend becomes an interesting goal. The present work is focused on commercial organic EVOO blends obtained by mixing multiple oils from different geographical origins. These blends have been studied by ¹H-NMR spectroscopy supported by multivariate statistical analysis. Specific characteristics of commercial organic EVOO blends originated by mixing oils from Italy, Tunisia, Portugal, Spain, and Greece were found to be associated with the increasing content of the Italian component. A linear progression of the metabolic profile defined characteristics for the analysed samples—up to a plateau level—was found in relation to the content of the main constituent of the Italian oil, the monocultivar Coratina. The Italian constituent percentage appears to be correlated with the fatty acids (oleic) and the polyphenols (tyrosol, hydroxytyrosol, and derivatives) content as major and minor components respectively. These results, which highlight important economic aspects, also show the utility of ¹H-NMR associated with chemometric analysis as a powerful tool in this field. Mixing oils of different national origins, to obtain blends with specific characteristics, could be profitably controlled by this methodology.     

Recent Advances in Recovery of Lycopene from Tomato Waste: A Potent Antioxidant with Endless Benefits

Growing attention to environmental protection leads food industries to adopt a model of “circular economy” applying safe and sustainable technologies to recover, recycle and valorize by-products. Therefore, by-products become raw material for other industries. Tomato processing industry produces significant amounts of by-products, consisting of skins and seeds. Tomato skin is very rich in lycopene, and from its seeds, high nutritional oil can be extracted. Alternative use of the two fractions not only could cut disposal costs but also allow one to extract bioactive compounds and an oil with a high nutritional value. This review focused on the recent advance in extraction of lycopene, whose beneficial effects on health are widely recognized.     

Cell protection from Ca2+-overloading by bioactive molecules extracted from olive pomace

We are reporting in the present study that molecules extracted from olive pomace prevent cell death induced by Ca²⁺-overloading in different cell types. Exposure of cells to these molecules counteracts the Ca²⁺-induced cell damages by reducing the activation of the Ca²⁺-dependent protease calpain, acting possibly through the modification of the permeability to Ca²⁺ of the plasma membrane. The purification step by RP-HPLC suggests that effective compound(s), differing from the main biophenols known to be present in the olive pomace extract, could be responsible for this effect. Our observations suggest that bioactive molecules present in the olive pomace could be potential candidates for therapeutic applications in pathologies characterised by alterations of intracellular Ca²⁺ homeostasis.     

Carbon and nitrogen distribution in the sediments of lagoon of Ravenna (Italy)

The distribution and the origin of carbon and nitrogen in sediments of an Italian lagoon--located north-east of Ravenna town--were investigated. From 1957 to 1976, the lagoon had been affected by a strong industrial pollution due to an important petrochemical complex. At present, industrial and domestic waste waters undergo a treatment process before being discharged into the lagoon. Sediment samples from 10 locations throughout the lagoon were analysed, in order to document the spatial and vertical distribution of C and N. Data show a very strong variability (organic carbon content varies between 8.9% and 0.14%) and the highest values were found in the immediate vicinity of the industrial discharge. Sediment organic matter shows allochthonous origin in proximity of industrial discharge and autochthonous origin in the remaining areas.     

Complexes of Al(III) with d-gluconic acid

The complexation of Al(III) with d-gluconic acid was studied in solution by means of pH-potentiometry, ESI mass spectrometry and one- and two-dimensional NMR spectroscopy. Six complexes were found to form in solution from pH 2 to 10: [AlL]²⁺, [AlLH₋₁]⁺, [AlLH₋₂], [AlLH₋₃]⁻, [AlL₂H₋₁] and [AlL₂H₋₂]⁻. NMR spectroscopy indicated very complicated chemical exchange processes between the free ligand and gluconic acid molecules bound in the metal complexes, with different coordination modes resulting in changes both of the chemical shift and of the line shape of the signals. A solid complex [AlL₂H₋₁] · 2H₂O was isolated as a microcrystalline powder and characterized. The structures of the complexes are discussed on the basis of the spectroscopic results and MM force field calculations.     

Semi-preparative HPLC purification of δ-tocotrienol (δ-T3) from Elaeis guineensis Jacq. and Bixa orellana L. and evaluation of its in vitro anticancer activity in human A375 melanoma cells

In this work, we report a rapid and convenient HPLC-UV-DAD method for the isolation of δ-T3 on semi-preparative scale from two different vitamin E rich processed, commercially available products obtained from the fruits of Elaeis guineensis Jacq. (oil palm) and from the seeds of Bixa orellana L. (achiote tree). Chromatography was run using reverse phase (RP) C-18 columns and HPLC-grade acetonitrile as mobile phase. The purity of the isolated δ-T3, assessed by GC–MS and ¹H NMR was above 98%. The δ-T3 cytotoxic activity found in vitro against the proliferation of human A375 melanoma cells compared to that of the other δ-T3 free tocols mixture suggest its primary role in the experimental anticancer activity observed for palm oil derived products. Taken altogether, the results of this study highlight the importance of the application of suitable purification systems for the preparations of tocotrienols prior to their experimental or clinical testing.