Selenides and diselenides containing oxadiazoles: a new class of functionalised materials

A simple and efficient procedure for the synthesis of a new class of organoselenium liquid crystal compounds was developed. The coupling of aryl bromides with elemental selenium was catalysed using copper oxide nanopowder in the presence of potassium hydroxide employing dimethyl sulfoxide as the solvent. This is the first report of the synthesis and characterisation of liquid crystal-based diselenides. Their mesophases were characterised by polarising optical microscopy and differential scanning calorimetry. Compounds 1, 2 and 4b exhibited the smectic A phase. In addition, these compounds showed weak blue fluorescence in solution (λ_{max. em.} 350–405 nm) and a Stokes shift of around 90 nm.     

Metabolomic Profiling of Fresh Goji (Lycium barbarum L.) Berries from Two Cultivars Grown in Central Italy: A Multi-Methodological Approach

The metabolite profile of fresh Goji berries from two cultivars, namely Big Lifeberry (BL) and Sweet Lifeberry (SL), grown in the Lazio region (Central Italy) and harvested at two different periods, August and October, corresponding at the beginning and the end of the maturation, was characterized by means of nuclear magnetic resonance (NMR) and electrospray ionization Fourier transform ion cyclotron resonance (ESI FT-ICR MS) methodologies. Several classes of compounds such as sugars, amino acids, organic acids, fatty acids, polyphenols, and terpenes were identified and quantified in hydroalcoholic and organic Bligh-Dyer extracts. Sweet Lifeberry extracts were characterized by a higher content of sucrose with respect to the Big Lifeberry ones and high levels of amino acids (glycine, betaine, proline) were observed in SL berries harvested in October. Spectrophotometric analysis of chlorophylls and total carotenoids was also carried out, showing a decrease of carotenoids during the time. These results can be useful not only to valorize local products but also to suggest the best harvesting period to obtain a product with a chemical composition suitable for specific industrial use. Finally, preliminary studies regarding both the chemical characterization of Goji leaves generally considered a waste product, and the biological activity of Big Lifeberry berries extracts was also investigated. Goji leaves showed a chemical profile rich in healthy compounds (polyphenols, flavonoids, etc.) confirming their promising use in the supplements/nutraceutical/cosmetic field. MG63 cells treated with Big Lifeberry berries extracts showed a decrease of iNOS, COX-2, IL-6, and IL-8 expression indicating their significant biological activity.     

Chain Dominated Orders

We study finite partial orders which have a chain such that every element of the order either belongs to this chain or has all its covers in this chain. We show that such orders are exactly the orders being both interval orders and truncated lattices. We prove that their jump number is polynomially tractable and that their dimension is unbounded. We also show that every order admits a visibility model having such an order as host.     

Computing on-line the lattice of maximal antichains of posets

We consider the on-line computation of the lattice of maximal antichains of a finite poset . This on-line computation satisfies what we call the linear extension hypothesis: the new incoming vertex is always maximal in the current subposet of . In addition to its theoretical interest, this abstraction of the lattice of antichains of a poset has structural properties which give it interesting practical behavior. In particular, the lattice of maximal antichains may be useful for testing distributed computations, for which purpose the lattice of antichains is already widely used. Our on-line algorithm has a run time complexity of , where |P| is the number of elements of the poset, , |MA(P)| is the number of maximal antichains of and (P) is the width of . This is more efficient than the best off-line algorithms known so far.     

Towards the reconstruction of posets

The reconstruction conjecture for posets is the following: Every finite posetP of more than three elements is uniquely determined — up to isomorphism — by its collection of (unlabelled) one-element-deleted subposets P–{x}:xV(P).We show that disconnected posets, posets with a least (respectively, greatest) element, series decomposable posets, series-parallel posets and interval orders are reconstructible and that N-free orders are recognizable.We show that the following parameters are reconstructible: the number of minimal (respectively, maximal) elements, the level-structure, the ideal-size sequence of the maximal elements, the ideal-size (respectively, filter-size) sequence of any fixed level of the HASSE-diagram and the number of edges of the HASSE-diagram.This is considered to be a first step towards a proof of the reconstruction conjecture for posets.Research partly supported by DAAD.     

Fe(III)-Catalyzed direct C3 chalcogenylation of indole: The effect of iodide ions

A mild and efficient iron (III)-catalyzed C3 chalcogenylation of indoles has been developed and the role of the iodide ions in this transformation was investigated. EPR experiments revealed the reduction of Fe(III) to Fe(II) under the reaction conditions, supporting the formation of molecular iodine in the system, which in effect catalyze the reaction. The scope of the chalcogenylation was broad and the synthesis of more functionalized 3-selenylindoles was explored.     

Infrared-Assisted Synthesis of Prebiotic Glycine

A novel approach has been developed to synthesize complex organic molecules (COMs) relevant to prebiotic chemistry, using infrared (IR) radiation to trigger the reaction. An original laboratory reactor working at low gas density and using IR irradiation was developed. In this way, glycine, the simplest brick of life, has been synthesized by assisting ion–molecule reaction with IR laser light. The ion-molecule complex constituted by acetic acid and hydroxylamine was formed in a mass spectrometer reactor and then irradiated with IR photons. As photoproducts, we obtained both glycine structures and some of its isomers. Anharmonic vibrational frequency calculations and fragmentation dynamics simulations allow for a better interpretation of the experimental data. This novel approach can be now extended to study other new synthetic pathways responsible for the formation of further COMs also with potential prebiotic relevance.     

Combined Experimental and Simulation Studies Suggest a Revised Mode of Action of the Anti‐Alzheimer Disease Drug NQ‐Trp

Inhibition of the aggregation of the monomeric peptide β‐amyloid (Aβ) into oligomers is a widely studied therapeutic approach in Alzheimer’s disease (AD). Many small molecules have been reported to work in this way, including 1,4‐naphthoquinon‐2‐yl‐L ‐tryptophan (NQ‐Trp). NQ‐Trp has been reported to inhibit aggregation, to rescue cells from Aβ toxicity, and showed complete phenotypic recovery in an in vivo AD model. In this work we investigated its molecular mechanism by using a combined approach of experimental and theoretical studies, and obtained converging results. NQ‐Trp is a relatively weak inhibitor and the fluorescence data obtained by employing the fluorophore widely used to monitor aggregation into fibrils can be misinterpreted due to the inner filter effect. Simulations and NMR experiments showed that NQ‐Trp has no specific “binding site“‐type interaction with mono‐ and dimeric Aβ, which could explain its low inhibitory efficiency. This suggests that the reported anti‐AD activity of NQ‐Trp‐type molecules in in vivo models has to involve another mechanism. This study has revealed the potential pitfalls in the development of aggregation inhibitors for amyloidogenic peptides, which are of general interest for all the molecules studied in the context of inhibiting the formation of toxic aggregates.     

Partial Orders on Weak Orders Convex Subsets

We study a visibility relation on the nonempty connected convex subsets of a finite partially ordered set and we investigate the partial orders representable as a visibility relation of such subsets of a weak order. Moreover, we consider restrictions where the subsets of the weak order are total orders or isomorphic total orders.     

Line directionality of orders

Some orders can be represented by translating convex figures in the plane. It is proved thatN-free and interval orders admit such representations with an unbounded number of directions. Weak orders, tree-like orders and two-dimensional orders of height one are shown to be two- directional. In all cases line segments can be used as convex sets.