Hamiltonian structural analysis of curved beams with or without generalized two-parameter foundation

The solution of curved Timoshenko beams with or without generalized two-parameter elastic foundation is presented. Beam can be subjected to any kind of loads and imposed external actions, distributed or concentrated along the beam. It can have external and internal restraints and any kind of internal kinematical or mechanical discontinuity. Moreover, the beam may have any spatial curved geometry, by dividing the entire structure into segments of constant curvature and constant elastic properties, each segment resting or not on elastic foundation. The foundation has six parameters like a generalized Winkler soil with the addition of other two parameters involving the link between settlements in transverse direction, as occurs for Pasternak soil model. The solution is obtained by the Hamiltonian structural analysis method, based on an energetic approach, solving a mixed canonical Hamiltonian system of twelve differential equations, leading to the fundamental matrix. The solution, numerically expressed or in closed form, is fast and simple to be implemented on a software, being the solving matrix always of order 12 for any kind of geometry and loads, without increasing in computational complexity. Numerical examples are given, comparing the results of the proposed procedure with the literature data, for rectilinear and curved beams with different soil properties.     

Synthesis of 2′‐Deoxy‐1′‐homo‐N‐nucleosides with Anti‐Influenza Activity by Catalytic Methyltrioxorhenium (MTO)/H2O2 Oxyfunctionalization

This paper describes a new route for the synthesis of 1′‐homo‐N‐nucleoside derivatives by means of either methyltrioxorhenium (MTO) or supported MTO catalysts, with H₂O₂ as the primary oxidant. Under these selective conditions, the oxyfunctionalization of the heterocyclic ring and the N heteroatom oxidation were operative processes, regardless of the type of substrate used, that is, purine or pyrimidine derivatives. In addition, the oxidation of 1′‐homo‐N‐thionucleosides, showed the occurrence of site‐specific oxidative nucleophilic substitutions of the heterocyclic ring. The MTO/H₂O₂ system showed, in general, high reactivity under both homogeneous and heterogeneous conditions, affording the final products with high conversion values of substrates and from medium to high yields. Many of the novel 1′‐homo‐N‐nucleoside analogues were active against the influenza A virus, without any cytotoxic effects, retaining their activity in both protected and unprotected forms.     

Catalytic asymmetric reductive amination of aldehydes via dynamic kinetic resolution

A novel organocatalytic asymmetric reductive amination of aldehydes has been developed. Treating racemic alpha-branched aldehydes with p-anisidine and a Hantzsch ester in the presence of our previously developed phosphoric acid catalyst, TRIP, gave beta-branched secondary amines in excellent yields and enantioselectivities via an efficient dynamic kinetic resolution. The process is applicable to several different aromatic aldehydes and amines but gives slightly reduced enantiomeric ratios with aliphatic aldehydes.     

Facile synthesis of mosquitocidal silver nanoparticles using Mussaenda glabra leaf extract: characterisation and impact on non-target aquatic organisms

Plant-borne compounds have been proposed for extracellular synthesis of mosquitocidal nanoparticles. However, their impact against mosquito natural enemies has been scarcely studied. Here, we synthesised silver nanoparticles (Ag NPs) using Mussaenda glabra leaf extract as reducing and stabilising agent. Biofabricated Ag NPs were characterised by UV–vis spectrophotometry, X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Compared to the leaf aqueous extract, biosynthesised Ag NPs showed higher toxicity against mosquito vectors Anopheles subpictus, Aedes albopictus and Culex tritaeniorhynchus with LC₅₀ of 17–19 μg/mL, respectively. Ag NPs were found safer to non-target organisms Diplonychus indicus and Gambusia affinis, with respective LC₅₀ values ranging from 1446 to 8628 μg/mL. Overall, M. glabra-fabricated Ag NPs are a promising and eco-friendly tool against larval populations of mosquito vectors of medical and veterinary importance, with negligible toxicity against other non-target aquatic organisms.     

From the Hartree Dynamics to the Vlasov Equation

We consider the evolution of quasi-free states describing N fermions in the mean field limit, as governed by the nonlinear Hartree equation. In the limit of large N, we study the convergence towards the classical Vlasov equation. For a class of regular interaction potentials, we establish precise bounds on the 0rate of convergence.     

A copper thiolate centre for electron transfer: mononuclear vs. dinuclear complexes

We have structurally and spectroscopically investigated a rare example of a mononuclear aliphatic dithiolate Cu(II) complex characterized by a reversible Cu(II)/Cu(I) redox couple. By DFT, we have shown that this system has a lower reorganization energy than its previously described bis(μ-thiolato) dicopper parent complex, which reversibly cycles between the Cu(1.5)Cu(1.5) and Cu(I)Cu(I) redox states.     

Structural analysis of lignin in chestnut wood by pyrolysis-gas chromatography/mass spectrometry

The goal of the study was to determine the percentage of lignin in chestnut wood and to characterize structurally this polymer by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) according to a possible influence on ring shake defect. The sampling was performed in different sites of Lazio Region in Italy. Wood disks from trees with ring shake defect and without ring shake defect were selected and little amount of heartwood (1-2 g) sampled between 6th and 10th and between 11th and 15th annual growth ring were analyzed. The study allowed quantifying lignin content, which is in average 26% and syringyl/guaiacyl (S/G) ratio, which present an average value of 2.43. Belong the pyrolysis products of wood, the trees characterized by ring shake show a higher concentration of the phenol homosyringaldehyde respect to the healthy trees. There is not any evident difference in the products composition of pyrolysis in respect to trees’ age, especially the critical period of 12-14 years in which ring shake generally becomes more evident. The site of wood provenance is the higher factor of variability in the structure of lignin for many phenols.     

Profiling lithium distribution in Sn anode for lithium-ion batteries with neutrons

Measuring the distribution of lithium in high capacity lithium-ion battery (LIB) electrodes is essential to understanding the coulombic losses during the lithiation/delithiation processes that occur while charging and discharging the cell. In this research, two half-cell prototypes were fabricated by electrochemically lithiating Sn foil anodes in 1M LiBF₄ in a 1:1 (wt:wt) ethylene carbonate and dimethyl carbonate solutions at a constant potential of 0.50 and 0.67 V (vs. Li/Li⁺). The neutron depth profiling (NDP) technique was employed to study the Li distributions in the anodes. Li concentration profiles were resolved for the samples lithiated under different conditions for LIB studies. In addition, this paper demonstrated an in situ NDP measurement of an electrochemical cell with a thin window design, which reveals the dynamics of lithium distribution within the Sn anode.     

A simple acylation of thiols with anhydrides

Different thiols were efficiently acylated at room temperature with different anhydrides in the presence of potassium carbonate. Chemoselective protection of thiol in the presence of hydroxy group was achieved using di-tert-butyl dicarbonate and isatoic anhydride.     

Rapid and convenient semi-automated microwave-assisted solid-phase synthesis of arylopeptoids

A facile and expedient route to the synthesis of arylopeptoid oligomers (N-alkylated aminomethyl benz-amides) using semi-automated microwave-assisted solid-phase synthesis is presented. The synthesis was optimized for the incorporation of side chains derived from sterically hindered or unreactive amines and both ortho- and para-substituted arylo-backbones. By utilizing this optimized protocol a complex nonameric arylopeptoid was synthesized in less than 11 h, featuring a novel alternating ortho-, meta-, and para-substituted backbone pattern and a variety of chemically diverse and challenging side chains.