Easy access to 4-nitrothiochroman S,S-dioxides via ring-enlargement from 3-nitrobenzo[b]thiophene

The (E)-2-aryl-1-[2-(methylthio)phenyl]-1-nitroethylenes 5 can easily be oxidized to the relevant sulfones 6 and effectively subjected to cyclization via an intramolecular Michael addition after metallation with lithium bis(trimethylsilyl)amide in THF. After quenching with ammonium chloride the 3-aryl-4-nitrothiochroman S,S-dioxides 2 are obtained as diastereomeric mixtures in good to excellent yields. Both yields and stereochemistry of the ring-closure step appear to be influenced by steric effects of the 3-aryl moiety. As sulfides 5 derive from an initial ring opening of 3-nitrobenzo[b]thiophene (1), the overall 1 to 2 process can be considered as an effective 5 to 6 ring enlargement of the sulfur heterocycle. A conformational ¹H NMR and molecular-mechanics investigation on the isolated diastereomeric 2 has also been accomplished.     

Speciation of heavy metals in sediments of the lagoon of Venice collected in the industrial area

In this study a procedure of sequential extraction of metals from sediments was applied to samples from the lagoon of Venice. Compared to the measurement of total concentrations, the knowledge of metal partitioning among sediment phases can help in estimating the risk posed by metal polluted sediments and give information on contamination sources and on the factors that influence metal enrichment in sediments. The results permitted to estimate for each metal the percentage of the total content that could be potentially remobilized from sediments, owing to changes in environmental conditions. The immediately available fraction represented in general a low proportion of the total content. An important proportion of most metals (except for Zn, Cd and Cu) was associated to residual phases and therefore was not expected to be released under the normal environmental conditions. The large amounts of metals bound to Fe-Mn oxides/hydroxides confirmed the strong scavenging efficiency of this phase. The carbonate phase was the preferential associative form for Pb, Cd and Zn, whereas Cu was bound in prevalence to the organic matter/sulphide phase.     

Lexicographic sums and fibre-faithful maps

The notion of lexicographic sum is introduced in general categories. Existence criteria are derived, particularly for locally cartesian closed categories and for categories with suitable coproducts. Lexicographic sums satisfy a generalized associative law. More importantly, every morphism can be factored through the lexicographic sum of its fibres. This factorization and the two types of maps arising from it, fibre-trivial and fibre-faithful, are studied particularly for partially ordered sets and forT ₁-spaces.     

Calix[4]arene-cholic acid conjugates: a new class of efficient synthetic ionophores

The synthesis of a new class of amphiphilic calix[4]arene-based ionophores, relying on direct reductive amination as a key step, and the evaluation of their H+ and Na+ transporting properties is described.     

Structure/function and phylogeny of hemoglobins of polar fishes

The northern and southern polar oceans have very different oceanographic features. Taking advantage of the information available on haemoglobin structure and function, we analysed the evolutionary history of the alpha and beta globins of Antarctic and Arctic haemoglobins as a basis for reconstructing the phylogenetic relationships among species.     

Bayesian analysis of in vivo dynamic 13C-edited 1H images

We propose an application of a Bayesian methodology to dynamic MR images of protons J-coupled to 13C nuclei for monitoring the in vivo 13C-glucose uptake of mouse brain. The very low population of these protons and the random noise make the analysis of these images extremely difficult. The proposed method restores the images and provides an "activation" map of the mouse brain by means of a hypothesis testing procedure. The restoration step is performed in the Bayesian framework so that among the other advantages of a stochastic approach, it is possible to model spatial and temporal information about neighboring pixels. This leads to a restoration procedure able to reduce the noise level while preserving the information about the edges of signal areas. Based on the restored images, the testing procedure provides us with a reliable map of pixels characterized by the 13C-glucose uptake.     

How to connect school mathematics with students' out-of-school knowledge

In this paper we present an explorative study for which special cultural artifacts have been used, i.e. supermarket receipts, to try to construct with 9-year old pupils (fourth class of primary school) a new mathematical knowledge, i.e. the algorithm for multiplication of decimal numbers. Furthermore also estimation and approximation processes have been introduced, procedures that are not commonly used in ordinary teaching activity. In our study the receipts, through some modifications, have become more explicitly tools of mediation and integration between in and out-of school knowledge, so they can be utilized to create new mathematical goals, thus becoming real mathematizing tools and constituting a didactic interface between in and out-of-school mathematics. In agreement with ethnomathematical perspective we deem that it is a task for the teacher to know, in order to be able to profitably take account of the teaching, the life experienced by the pupil. Future mathematics teachers should be prepared a) to see mathematics incorporated into real world, b) to investigate mathematical ideas and practices of their pupils, and c) to look for ways to incorporate into the curriculum elements belonging to the sociocultural environment of the pupils, as a starting point for mathematical activities in the classroom. In this way the motivation, interest and curiosity of the pupils will be increased and the attitude towards mathematics of both pupils and teachers will be changed.     

Hybrid Nanocomposite Films from Mono‐ and Multi‐Functional POSS Copolyacrylates in Miniemulsion

Summary: The synthesis of aqueous dispersions of hybrid acrylic copolymer particles with either a monofunctional or a multifunctional polyhedral oligomeric silsesquioxane methacrylate comonomer has been performed by free radical heterophase polymerization. The miniemulsion process gives stable latexes, whereas the less controlled emulsion route results in colloidal instability of the products. The thermal and mechanical properties of the nanocomposite latex films have been preliminarily investigated.

The nanocomposite latex particles based on hybrid copolyacrylates with highly dispersed POSS cages.     

Branched Polyethylenes by Cationic Benzyl Zirconium Heteroscorpionate Complexes: Role of the Borate Anion

Summary: A comparative study of the performances of (bpzmp)ZrBz₃ ( 1 ) and (hppzm)ZrBz₃ ( 2 ) activated with B(C₆F₅)₃ or [Ph₃C][B(C₆F₅)₄] in ethylene polymerisation pointed out that the steric properties of the metal complex and the boron activator affect the productivity of the catalyst and, more remarkably, the microstructure of the polyethylenes produced. A polymerisation mechanism accounting for these results has been proposed.

Structure of two heteroscorpionate zirconium complexes (bpzmp)ZrBz₃ ( 1 ) and (hppzm)ZrBz₃ ( 2 ).