General infinite dimensional duality and applications to evolutionary network equilibrium problems

In this paper the authors present an infinite dimensional duality theory for optimization problems and evolutionary variational inequalities where the constraint sets are given by inequalities and equalities. The difficulties arising from the structure of the constraint set are overcome by means of generalized constraint qualification assumptions based on the concept of quasi relative interior of a convex set. An application to a general evolutionary network model, which includes as special cases traffic, spatial price and financial equilibrium problems, concludes the paper.     

Formation and stability of proton-amine-inorganic anion complexes in aqueous solution

Interaction of some amines with inorganic ligands was studied potentiometrically in aqueous solutions at 25°C at different ionic strengths. The systems taken into account were: meta-PP, meta-TPP, en-PP, en-TPP, en-HPO ₄ ^2– , dap-SO ₄ ^2– , tetren-HPO ₄ ^2– , 6da-PP and 8da-TPP (meta=methylamine, en=ethylenediamine, tetren=tetraethylenepentamine, dap=1,2-diaminopropane, 6da=1,6-hexanediamine, 8da=1,8-octanediamine, PP=pyrophosphate, TPP=tripolyphosphate). Several ALH_r species are formed for all the studied mixed systems (A=amine, L =inorganic ligand), and in some cases A_pL_qH_r species were also found. The stability of mixed proton-ligand-ligand species is proportional to the charges involved in the complexation reaction and, to some extent, it depends on steric characteristic of the ligands. A simple relationship has been found between formation constants of mixed ligand species and charges involved in the complexation reaction. The ionic strength dependence of formation constants has been taken into account, and it was found that, also for these types of mixed complexes, a general equation independent of the nature of the reactants can be used.     

Synthesis of new 2,2′‐disubstituted 5,5′‐dimethyl‐4,4′‐bitriazoles and 2‐(4‐Triazolyl)quinoxalines

Thermal rearrangement of 3‐acylisoxazole arylhydrazones allowed facile preparation of 2H‐1,2,3‐triazoles which were firstly reacted with isoamyl nitrite and then with an opportune arylhydrazine to produce the corresponding α‐hydroxyiminohydrazones 8a‐h . The reaction of compounds 8a‐h with phosphorus pentachloride afforded the desired 4,4′‐bitriazoles 1a‐h . The α‐hydroxyiminoketone derivative 7 or the α‐diketone 14 reacted easily with 1,2‐phenylenediamine to afford 1,2,3‐triazoles 2a‐c bearing the quinoxaline moiety at position 4. Improved yields of the quinoxalines 2a‐c were obtained when 1,2‐phenylenediamine was reacted with the dioxime 15.     

Structural adaptation of the subunit interface of oligomeric thermophilic and hyperthermophilic enzymes

Enzymes from thermophilic and, particularly, from hyperthermophilic organisms are surprisingly stable. Understanding of the molecular origin of protein thermostability and thermoactivity attracted the interest of many scientist both for the perspective comprehension of the principles of protein structure and for the possible biotechnological applications through application of protein engineering. Comparative studies at sequence and structure levels were aimed at detecting significant differences of structural parameters related to protein stability between thermophilic and hyperhermophilic structures and their mesophilic homologs. Comparative studies were useful in the identification of a few recurrent themes which the evolution utilized in different combinations in different protein families. These studies were mostly carried out at the monomer level. However, maintenance of a proper quaternary structure is an essential prerequisite for a functional macromolecule. At the environmental temperatures experienced typically by hyper- and thermophiles, the subunit interactions mediated by the interface must be sufficiently stable. Our analysis was therefore aimed at the identification of the molecular strategies adopted by evolution to enhance interface thermostability of oligomeric enzymes. The variation of several structural properties related to protein stability were tested at the subunit interfaces of thermophilic and hyperthermophilic oligomers. The differences of the interface structural features observed between the hyperthermophilic and thermophilic enzymes were compared with the differences of the same properties calculated from pairwise comparisons of oligomeric mesophilic proteins contained in a reference dataset. The significance of the observed differences of structural properties was measured by a t-test. Ion pairs and hydrogen bonds do not vary significantly while hydrophobic contact area increases specially in hyperthermophilic interfaces. Interface compactness also appears to increase in the hyperthermophilic proteins. Variations of amino acid composition at the interfaces reflects the variation of the interface properties.     

Ring inversion dynamics of derivatives of thianthrene di- and tetraoxide

The ring inversion barrier for thianthrene tetraoxide was determined by making use of the variable temperature 13C NMR spectra of the 2,7-diisopropyl derivative (DeltaG(double dagger) = 6.5 kcal mol(-1)). The barrier is lower than that measured for a trans thianthrene dioxide derivative (DeltaG(double dagger) = 9.35 kcal mol(-1)). These results agree well with ab initio theoretical predictions.     

Improving the Phloroglucinolysis Protocol and Characterization of Sagrantino Wines Proanthocyanidins

Proanthocyanidins are key metabolites that explain wine sensorial character (bitterness and astringency) and red wine color changes during aging. Therefore, a fast and accurate method to evaluate the degree of polymerization and the structural composition of the polymeric proanthocyanidins is a crucial analytical tool. Phloroglucinolysis is the most used method for this analysis but, unfortunately, the phloroglucinol adducts of the monomeric flavan-3-ols are not commercially available, making the results less accurate. The aim of this work was the isolation by semi-preparative high performance liquid chromatography (HPLC) of these non-commercial compounds and their use for the development of an accurate UHPLC-MS/MS protocol. The purity of each adduct was established via quantitative ¹H-nuclear magnetic resonance (NMR) measurements with 3-trimethylsilyl-propionic-d4 acid sodium salt as the calibration standard. The developed method was applied to evaluate the proanthocyanidins profile of Sagrantino di Montefalco wines in comparison to other well-known tannic wines. Commercial, 6–8 years old Sagrantino wines were demonstrated to be very rich in epicatechin type B procyanidins, to have low galloylation %, and to have a high mean degree of polymerization of the proanthocyanidins with respect to the other analyzed wines.     

Photo‐biocatalytic One‐Pot Cascades for the Enantioselective Synthesis of 1,3‐Mercaptoalkanol Volatile Sulfur Compounds

The synthesis of enantiomerically pure 1,3‐mercaptoalkanol volatile sulfur compounds through a one‐pot photo‐biocatalytic cascade reaction is described. Two new KRED biocatalysts with opposite enantioselectivity were discovered and proved to be efficient on a wide range of substrates. The one‐pot cascade reaction combining photocatalytic thio‐Michael addition with biocatalytic ketoreduction in an aqueous medium provides a green and sustainable approach to enantiomerically pure 1,3‐mercaptoalkanols in high yields with excellent enantioselectivity.     

The Structure of Sub‐nm Platinum Clusters at Elevated Temperatures

Little is known about metallic clusters consisting merely of a dozen of atoms or even less, despite of their importance in catalysis and crystal nucleation. Scanning transmission electron microscopy (STEM) provides direct atomic structure information but has inherently suffered from limited time resolution. We employ fast dynamic STEM combined with a spatio‐temporal image denoising algorithm to explore the structure and stability of Pt clusters on carbon, which represents a highly relevant catalysis system. At room temperature, dynamic amorphous 2D structures are found, while above ≈300 °C, the clusters transform into a crystalline state. Our experimental and theoretical data reveal an unexpected strong trend of the crystalline clusters to exhibit the face‐centered cubic, bulk structure of Pt with cuboidal geometries being most prominent.     

Integral toxicity test of sea waters by an algal biosensor

An integral toxicity test, based on an algal biosensor and suitable to be used in sea water, is presented. The biosensor was designed and built by coupling a Clark oxygen electrode as transducer and the marine alga Spirulina subsalsa as biological mediator; it constitutes the "core" in a lab-scale prototype of a flow apparatus suitable to continuously monitor, in sea water, the photosynthetic activity of the alga and, from its variation, the marine pollution from the toxicological point of view. Inorganic pollutants (heavy metals) were tested in previous researches while organic ones (chlorophenols, pesticides and surfactants) are the object of the present paper.