A mechanical model for heat conduction

Continuum Mechanics and Thermodynamics - A theory of heat conduction in rigid heat conductors based entirely on mechanical concepts is proposed and compared with the traditional thermodynamic...     

A Ruthenium(II)–Copper(II) Dyad for the Photocatalytic Oxygenation of Organic Substrates Mediated by Dioxygen Activation

Dioxygen activation by copper complexes is a valuable method to achieve oxidation reactions for sustainable chemistry. The development of a catalytic system requires regeneration of the Cu^I active redox state from Cu^II. This is usually achieved using extra reducers that can compete with the Cu^II(O₂) oxidizing species, causing a loss of efficiency. An alternative would consist of using a photosensitizer to control the reduction process. Association of a Ru^II photosensitizing subunit with a Cu^II pre‐catalytic moiety assembled within a unique entity is shown to fulfill these requirements. In presence of a sacrificial electron donor and light, electron transfer occurs from the Ru^II center to Cu^II. In presence of dioxygen, this dyad proved to be efficient for sulfide, phosphine, and alkene catalytic oxygenation. Mechanistic investigations gave evidence about a predominant ³O₂ activation pathway by the Cu^I moiety.     

Dipolar Rotors Orderly Aligned in Mesoporous Fluorinated Organosilica Architectures

New mesoporous covalent frameworks, based on hybrid fluorinated organosilicas, were prepared to realize a periodic architecture of fast molecular rotors containing dynamic dipoles in their structure. The mobile elements, designed on the basis of fluorinated p‐divinylbenzene moieties, were integrated into the robust covalent structure through siloxane bonds, and showed not only the rapid dynamics of the aromatic rings (ca. 10⁸ Hz at 325 K), as detected by solid‐state NMR spectroscopy, but also a dielectric response typical of a fast dipole reorientation under the stimuli of an applied electric field. Furthermore, the mesochannels are open and accessible to diffusing in gas molecules, and rotor mobility could be individually regulated by I₂ vapors. The iodine enters the channels of the periodic structure and reacts with the pivotal double bonds of the divinyl‐fluoro‐phenylene rotors, affecting their motion and the dielectric properties.     

Microporous Molecular Materials from Dipeptides Containing Non‐proteinogenic Residues

Dipeptides with two hydrophobic side chains have proved to be an exceptional source of microporous organic materials, but since previous structures were limited to the incorporation of only proteinogenic residues, their full potential as adsorbents has remained unexplored. Single‐crystal XRD data for ten new compounds with non‐proteinogenic L ‐2‐aminobutanoic acid and/or L ‐2‐amino‐pentanoic acid are presented. The gas‐phase accessibility of their crystal pores, with cross‐sections of 2.3 to 5.1 Å, was monitored by CO₂ and CH₄ adsorption isotherms. Included CO₂ was also detected spectroscopically by 2D MAS NMR. An extensive conformational analysis reveals that the use of linear rather than branched side chains (such as L ‐valine and L ‐isoleucine) affords peptides with a greater degree of conformational freedom and yields more‐flexible channel surfaces that may easily adapt to a series of potential guest molecules.     

Smart Coatings Prepared via MAPLE Deposition of Polymer Nanocapsules for Light-Induced Release

Herein, smart coatings based on photo-responsive polymer nanocapsules (NC) and deposited by laser evaporation are presented. These systems combine remotely controllable release and high encapsulation efficiency of nanoparticles with the easy handling and safety of macroscopic substrates. In particular, azobenzene-based NC loaded with active molecules (thyme oil and coumarin 6) were deposited through Matrix-Assisted Pulsed Laser Evaporation (MAPLE) on flat inorganic (KBr) and organic (polyethylene, PE) and 3D (acrylate-based micro-needle array) substrates. SEM analyses highlighted the versatility and performance of MAPLE in the fabrication of the designed smart coatings. DLS analyses, performed on both MAPLE- and drop casting-deposited NC, demonstrated the remarkable adhesion achieved with MAPLE. Finally, thyme oil and coumarin 6 release experiments further demonstrated that MAPLE is a promising technique for the realization of photo-responsive coatings on various substrates.     

Binding free energy predictions in host-guest systems using Autodock4. A retrospective analysis on SAMPL6, SAMPL7 and SAMPL8 challenges

Journal of Computer-Aided Molecular Design - We systematically tested the Autodock4 docking program for absolute binding free energy predictions using the host-guest systems from the recent SAMPL6,...     

A priori bounds for the plastic dissipation of elastic-plastic oscillators

Summary The possibility of enlarging the definition of collapse of elastic-plastic structures to include dynamic problems is first examined. It is concluded that the most satisfactory definition is the one given in terms of plastic dissipation. The simple case of a single-degree of freedom oscillator is then studied in detail. After giving some upper bounds for the dissipation with the aid of suitable a priori inequalities, a typical property of stability of the solution is employed to obtain a fairly severe bracketing of velocities throughout the motion. A numerical example, taken from a problem of seismic design, shows that the latter result leads to further improvements in majorizing the plastic dissipation.

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Sommario Si studia aapprima l'estensione della definizione di collasso di una struttura elastoplastica ai problemi di tipo dinamico, concludendo che la miglior caratterizzazione é quella in termini di dissipazione plastica. Si passa poi a considerare il caso di un oscillatore a un grado di libertà, per cui si calcolano limitazioni superiori della dissipazione ricorrendo a opportune diseguaglianze a priori. Utilizzando inoltre una proprietà di stabilità della soluzione, tipica dei problemi di Plasticità, si riescono a dare strette limitazioni per la velocità. Come mostrato da un esempio numerico tratto da un problema sismico, esse conducono anche ad una più accurata delimitazione della dissipazione plastica.

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This research was supported in part by the C.N.R., Gruppo Nazionale per la Fisica Matematica e per le Applicazioni della Matematica alla Fisica e all'Ingegneria.     

The added mass of a deformable cylinder moving in a liquid

Let an infinitely long cylinder move perpendicular to its length in an infinite mass of liquid which is at rest at infinity. If the cylinder is rigid, the whole effect of the presence of the liquid may be represented by adding to the inertia per unit length of the solid cylinder the mass per unit length of the displaced fluid. If, however, the cylinder is elastically deformable, the mass of the moving fluid depends on the change in shape of the, initially circular, cross-sections of the cylinder. Thus the added mass is no longer a constant, but a function of the pressure exerted by the fluid on the solid cylinder.