Carba-D,L-allal- and -D,L-galactal-derived vinyl N-nosyl aziridines as useful tools for the synthesis of 4-deoxy-4-(N-nosylamino)-2,3-unsaturated-5a-carbasugars

The novel carba-D,L-allal- and carba-D,L-galactal-derived vinyl N-nosyl aziridines were prepared and the regio- and stereoselective behavior in opening reactions with O- and N-nucleophiles examined. The carbaglycosylating ability of the novel aziridines, as deduced by the amount of 1,4-addition products (1,4-regioselectivity) obtained in the acid-catalyzed methanolysis taken as a model reaction, is similar or superior to that observed with the corresponding carba-D,L-allal- and -D,L-galactal-derived vinyl epoxides, respectively. In all 1,2- and 1,4-addition products obtained, a –(N-nosylamino) group is regio- and stereoselectively introduced at the C(4) carbon of a 1,2- or 2,3-unsaturated carbasugar, susceptible to further elaborations toward aminocyclitol derivatives. The stereoselective synthesis of the corresponding, enantiomerically pure carba-D,L-allal- and -D,L-galactal-derived vinyl N-acetyl aziridines is also described

Closest-vector problem and the zero-temperature p-spin landscape for lossy compression

We consider a high-dimensional random constrained optimization problem in which a set of binary variables is subjected to a linear system of equations. The cost function is a simple linear cost, measuring the Hamming distance with respect to a reference configuration. Despite its apparent simplicity, this problem exhibits a rich phenomenology. We show that different situations arise depending on the random ensemble of linear systems. When each variable is involved in at most two linear constraints, we show that the problem can be partially solved analytically, in particular we show that upon convergence, the zero-temperature limit of the cavity equations returns the optimal solution. We then study the geometrical properties of more general random ensembles. In particular we observe a range in the density of constraints at which the system enters a glassy phase where the cost function has many minima. Interestingly, the algorithmic performances are only sensitive to another phase transition affecting the structure of configurations allowed by the linear constraints. We also extend our results to variables belonging to GF(q), the Galois field of order q. We show that increasing the value of q allows to achieve a better optimum, which is confirmed by the replica-symmetric cavity method predictions

Unprecedented catalytic enantioselective trapping of arene oxides with dialkylzinc reagents

The first catalytic enantioselective trapping of symmetrical and racemic arene oxides with organometallic reagents is reported.

A new catalytic and enantioselective desymmetrization of symmetrical methylidene cycloalkene oxides

Chiral copper complexes of C2-symmetrical hosphoroamidites were found to be highly effective catalysts for both kinetic resolution and novel desymmetrization reactions of new methylidene epoxycycloalkanes.

Microbial assisted phytodepuration for water reclamation: Environmental benefits and threats

Climate changes push for water reuse as a priority to counteract water scarcity and minimize water footprint especially in agriculture, one of the highest water consuming human activities. Phytodepuration is indicated as a promising technology for water reclamation, also in the light of its economic and ecological sustainability, and the use of specific bacterial inocula for microbial assisted phytodepuration has been proposed as a further advance for its implementation. Here we provided an overview on the selection and use of plant growth promoting bacteria in Constructed Wetland (CW) systems, showing their advantages in terms of plant growth support and pollutant degradation abilities. Moreover, CWs are also proposed for the removal of emerging organic pollutants like antibiotics from urban wastewaters. We focused on this issue, still debated in the literature, revealing the necessity to deepen the knowledge on the antibiotic resistance spread into the environment in relation to treated wastewater release and reuse. In addition, given the presence in the plant system of microhabitats (e.g. rhizosphere) that are hot spot for Horizontal Gene Transfer, we highlighted the importance of gene exchange to understand if these events can promote the diffusion of antibiotic resistance genes and antibiotic resistant bacteria, possibly entering in the food production chain when treated wastewater is used for irrigation. Ideally, this new knowledge will lead to improve the design of phytodepuration systems to maximize the quality and safety of the treated effluents in compliance with the 'One Health' concept

One-pot multi-enzymatic synthesis of the four stereoisomers of 4-methylheptan-3-ol

The use of pheromones in the integrated pest management of insects is currently considered a sustainable and environmentally benign alternative to hazardous insecticides. 4-Methylheptan-3-ol is an interesting example of an insect pheromone, because its stereoisomers are active towards different species. All four possible stereoisomers of this compd. were prepd. from 4-methylhept-4-en-3-one by a one-pot procedure in which the two stereogenic centers were created during two sequential redns. catalyzed by an ene-reductase (ER) and an alc. dehydrogenase (ADH), resp