Metal-organic chains constructed from pre-organized N2S2 donor ligands

Three new N₂S₂ donor ligands 1,1′-((2-(2-(phenylthio)phenylthio)phenyl)methylene)bis(3,5-R-1H-pyrazole), R = H (L^H), R = Me (L^Me), R = i-Pr (L^i-Pr) have been prepared and characterized. These bifunctional ligands incorporate two distinct chelate donor systems, by virtue of the presence of bispyrazole and bisthioether functions. The preferred conformation of these ligands is such that the N₂ and S₂ donor moieties may be oriented in opposite directions, thus favoring the formation of molecular chains when treated with AgBF₄. The X-ray structures of Ag(I) complexes show that, depending on the steric hindrance present on the pyrazole rings, these ligands behave as κ⁴-SSNN-μ bridging tetradentate (when R = H), or κ³-SNN-μ bridging tridentate (when R = Me, i-Pr). Interestingly, [Ag(L^H)]BF₄ crystallizes in the chiral space group P4₁, with the molecular chain that is folded around the 4₁ screw axis.     

Ginzburg–Landau functionals and renormalized energy: A revised Γ-convergence approach

We give short and self-contained proofs of Γ-convergence results for Ginzburg–Landau energy functionals in two dimensions, in the logarithmic energetic regime. In particular, we derive the renormalized energy by Γ-convergence.     

Approximate dynamic programming for stochastic N-stage optimization with application to optimal consumption under uncertainty

Stochastic optimization problems with an objective function that is additive over a finite number of stages are addressed. Although Dynamic Programming allows one to formally solve such problems, closed-form solutions can be derived only in particular cases. The search for suboptimal solutions via two approaches is addressed: approximation of the value functions and approximation of the optimal decision policies. The approximations take on the form of linear combinations of basis functions containing adjustable parameters to be optimized together with the coefficients of the combinations. Two kinds of basis functions are considered: Gaussians with varying centers and widths and sigmoids with varying weights and biases. The accuracies of such suboptimal solutions are investigated via estimates of the error propagation through the stages. Upper bounds are derived on the differences between the optimal value of the objective functional and its suboptimal values corresponding to the use at each stage of approximate value functions and approximate policies. Conditions under which the number of basis functions required for a desired approximation accuracy does not grow “too fast” with respect to the dimensions of the state and random vectors are provided. As an example of application, a multidimensional problem of optimal consumption under uncertainty is investigated, where consumers aim at maximizing a social utility function. Numerical simulations are provided, emphasizing computational pros and cons of the two approaches (i.e., value-function approximation and optimal-policy approximation) using the above-mentioned two kinds of basis functions. To investigate the dependencies of the performances on dimensionality, the numerical analysis is performed for various numbers of consumers. In the simulations, discretization techniques exploiting low-discrepancy sequences are used. Both theoretical and numerical results give insights into the possibility of coping with the curse of dimensionality in stochastic optimization problems whose decision strategies depend on large numbers of variables.     

Iodosobenzene Diacetate and Diphenyl Diselenide: An Electrophilic Selenenylating Agent of Double Bonds

Phenylseleno-acetoxylation, hydroxylation, etherification and lactonization products are obtained in good yields from the reaction of alkenes with diphenyl diselenide and iodosobenzene diacetate, in acetonitrile.

     

Flexural-torsional bifurcations of a cantilever beam under potential and circulatory forces I: Non-linear model and stability analysis

The stability of a cantilever elastic beam with rectangular cross-section under the action of a follower tangential force and a bending conservative couple at the free end is analyzed. The beam is herein modeled as a non-linear Cosserat rod model. Non-linear, partial integro-differential equations of motion are derived expanded up to cubic terms in the transversal displacement and torsional angle of the beam. The linear stability of the trivial equilibrium is studied, revealing the existence of buckling, flutter and double-zero critical points. Interaction between conservative and non-conservative loads with respect to the stability problem is discussed. The critical spectral properties are derived and the corresponding critical eigenspace is evaluated.     

Minimising movements for the motion of discrete screw dislocations along glide directions

In Alicandro et al. (J Mech Phys Solids 92:87–104, 2016) a simple discrete scheme for the motion of screw dislocations toward low energy configurations has been proposed. There, a formal limit of such a scheme, as the lattice spacing and the time step tend to zero, has been described. The limiting dynamics agrees with the maximal dissipation criterion introduced in Cermelli and Gurtin (Arch Ration Mech Anal 148, 1999) and predicts motion along the glide directions of the crystal. In this paper, we provide rigorous proofs of the results in [3], and in particular of the passage from the discrete to the continuous dynamics. The proofs are based on \(\Gamma \)-convergence techniques.     

Dynamic Analysis of Linear and Nonlinear Oscillations of a Beam Under Axial and Transversal Random Poisson Pulses

This paper proposes an approximate explicit probability density function for the analysis of external and parametric oscillation of a simply supported beam driven by random pulses. The impulsive loading model adopted is Poisson white noise, which is a process having Dirac delta occurrences with random intensity distributed in time according to Poisson's law. The response probability density function can be obtained by solving the related Kolmogorov–Feller integro-differential equation. An approximate solution is derived by transforming this equation to a first-order partial differential equation. The method of characteristics is then applied to obtain an explicit solution. The theory has been validated through numerical simulations.     

Electroless silver plating of the surface of organic semiconductors

The integration of nanoscale processes and devices demands fabrication routes involving rapid, cost-effective steps, preferably carried out under ambient conditions. The realization of the metal/organic semiconductor interface is one of the most demanding steps of device fabrication, since it requires mechanical and/or thermal treatments which increment costs and are often harmful in respect to the active layer. Here, we provide a microscopic analysis of a room temperature, electroless process aimed at the deposition of a nanostructured metallic silver layer with controlled coverage atop the surface of single crystals and thin films of organic semiconductors. This process relies on the reaction of aqueous AgF solutions with the nonwettable crystalline surface of donor-type organic semiconductors. It is observed that the formation of a uniform layer of silver nanoparticles can be accomplished within 20 min contact time. The electrical characterization of two-terminal devices performed before and after the aforementioned treatment shows that the metal deposition process is associated with a redox reaction causing the p-doping of the semiconductor.     

Electrochemical genosensors for the detection of Bonamia parasite. Selection of single strand-DNA (ssDNA) probes by simulation of the secondary structure folding

A post-PCR nucleic acid work by comparing experimental data, from electrochemical genosensors, and bioinformatics data, derived from the simulation of the secondary structure folding and prediction of hybridisation reaction, was carried out in order to rationalize the selection of ssDNA probes for the detection of two Bonamia species, B. exitiosa and B. ostreae, parasites of Ostrea edulis.Six ssDNA probes (from 11 to 25 bases in length, 2 thiolated and 4 biotinylated) were selected within different regions of B. ostreae and B. exitiosa PCR amplicons (300 and 304 bases, respectively) with the aim to discriminate between these parasite species. ssDNA amplicons and probes were analyzed separately using the “Mfold Web Server” simulating the secondary structure folding behaviour. The hybridisation of amplicon-probe was predicted by means of “Dinamelt Web Server”. The results were evaluated considering the number of hydrogen bonds broken and formed in the simulated folding and hybridisation process, variance in gaps for each sequence and number of available bases. In the experimental part, thermally denatured PCR products were captured at the sensor interface via sandwich hybridisation with surface-tethered probes (thiolated probes) and biotinylated signalling probes. A convergence between analytical signals and simulated results was observed, indicating the possibility to use bioinformatic data for ssDNA probes selection to be incorporated in genosensors.