Phytochemical analysis of non-volatile fraction of Artemisia caerulescens subsp. densiflora (Viv.) (Asteraceae), an endemic species of La Maddalena Archipelago (Sardinia – Italy)

Artemisia caerulescens subsp. densiflora Viv. is a rare endemic species from Corsica and Sardinia. We studied a sample collected from Razzoli, an island of the La Maddalena Archipelago. The polar secondary metabolites content of this species was investigated for the first time in this study showing the presence of sesquiterpenoids, flavonoids, caffeoylquinic acids and a coumarin, with the presence of several compounds already recognised in this genus. The metabolites composition was analysed in two different phenological stages, post blooming and flowering. During the blooming stage, the plant showed a molecular pattern mainly represented by sesquiterpenes and sterols with a minor amount of phenolics, while in flowering stage the molecular pattern was more rich in flavonoids and phenylpropanoids.     

Identifying key electrostatic interactions in Rhizomucor miehei lipase: the influence of solvent dielectric

The conformational change associated with the interfacial activation of Rhizomucor miehei lipase involves the displacement of an α-helical lid (residues 82–96) away from the active site on moving from water (high dielectric) to lipid (low dielectric). The presence of two media of very different dielectric properties suggests that electrostatic interactions play an important role in this process. We have used linearized Poisson–Boltzmann calculations to examine the key electrostatic interactions which contribute to lid stability in the closed and open states. It is the two charged residues of the lid, Arg86 and Asp91, that form the strongest electrostatic interactions with the rest of the protein. We identify key residues whose interactions with the lid are significantly perturbed by the change in the dielectric of the medium: Asp61, Arg80, Lys109, Glu117 and the active-site residues Asp203 and Asp256, all of which lie within approximately 20 ? of the lid. We suggest that these residues are good candidates for site-specific mutation studies, which could help elucidate their role in the lipase activation mechanism. Received: 27 May 1998 / Accepted: 17 September 1998 / Published online: 7 December 1998     

Synthesis and characterization of new polydiolcitrates with tunable properties

Polydiolcitrates are an emerging class of biocompatible polyesters with a great potential in the field of biomedicine and packaging for food and drug materials. In this work, a new type of (co‐)polydiolcitrates made of citric acid (CA) and ethylene glycol (EG) and/or poly(ethylene glycol) (PEG) is investigated. By varying both the EG/PEG and the CA/diol molar ratios, materials exhibiting very different swelling behavior, mechanical and thermal properties are obtained. In particular, the substitution of EG segments with longer and flexible PEG ones results in an increase in crosslinking density, with remarkable effects on swelling capacity, glass transition temperature, and Young modulus. Moreover, polyesters with CA/diol molar ratio equal to 1:1 exhibit shape memory properties, with full capacity of keeping the temporary shape and high capacity of recovering the original shape. This work demonstrates that the appropriate choice of polyester composition allows modulating the sample properties, that permits to these materials to cover a wide range of possible applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3713–3720     

Ru2+ complexes comprising terpyridine ligands appended with terthiophene chromophores: energy transfer and energy reservoir effect

Two Ru(2+) complexes containing terpyridine ligands appended with terthiophene units connected by a methyleneoxy or an alkynyl bridge show very different luminescent behaviours: the former is non-luminescent at 298 K owing to a photoinduced energy transfer process to the terthiophene moiety, while the latter exhibits an extraordinary long excited state lifetime because of an energy reservoir effect.     

Conformational analysis and UV/Vis spectroscopic properties of a rotaxane-based molecular machine in acetonitrile dilute solution: when simulations meet experiments

A reduced form of a synthetic hydrogen-assembled molecular shuttle for nano-technological applications has been investigated by molecular dynamics simulations and density functional theory calculations. It is composed by a benzylic amide macrocycle mechanically locked onto a thread in acetonitrile solution. Classical sampling indicates, in agreement with experimental findings, that in equilibrium condition at 298 K the macrocycle and the naphthalimide radical anion moiety within the thread strongly interact forming four strong OCN-H-O=CNR hydrogen bonds. Simulations also revealed that the geometry of the supramolecular assembly reversibly oscillates between unfolded and folded conformations, with the latter characterized by an electrostatic hook involving the succinamide end group and the macrocycle itself. Finally, the simulated UV-Vis absorption spectra for free and complexed reduced naphthalimide quantitatively confirm that the transient spectroscopic change experimentally used as a probe for monitoring the translational motion of the macrocycle, from succinamide to naphthalimide stations, accompanying the selective electrochemical reduction.     

Correlated trends of coexisting magnetism and superconductivity in optimally electron-doped oxypnictides

We report on the recovery of the short-range static magnetic order and on the concomitant degradation of the superconducting state in optimally F-doped SmFe(1-x)Ru(x)AsO(0.85)F(0.15) for 0.1≤x?0.5. The two reduced order parameters coexist within nanometer-size domains in the FeAs layers and eventually disappear around a common critical threshold x(c)~0.6. Superconductivity and magnetism are shown to be closely related to two distinct well-defined local electronic environments of the FeAs layers. The two transition temperatures, controlled by the isoelectronic and diamagnetic Ru substitution, scale with the volume fraction of the corresponding environments. This fact indicates that superconductivity is assisted by magnetic fluctuations, which are frozen whenever a short-range static order appears, and totally vanish above the magnetic dilution threshold x(c).     

Mechanical and thermal properties of a nanopowder talc compound produced by controlled ball milling

A powdered compound constituted by over the 95% of talc Mg₃Si₄O₁₀(OH)₂ with MgCO₃ and CaMg(CO₃)₂ as minor phases was mechanically deformed by compaction and shear to a nanosized particulate (crystallite size ~5 nm) in a specifically built planetary ball mill. The mechanical milling was conducted in a controlled thermodynamic environment (25 °C and 0.13 Pa) by using low mechanical load to minimise amorphisation of the material. Mechanical τ(ε) shear analysis and thermo-structural modifications of the nanostructured talc particulate were investigated after selected milling times (0, 1, 5 and 20 h). At the very early stages of milling (1 h) layer flattening, lamination and texturing of the talc particles occurred. For prolonged milling (up to 20 h), a progressive reduction of the TOT talc stacking layer coherence, from about 20–5 nm, and an increase of (001) microstrain from about 0.6–2.2 × 10⁻² nm, as a non-linear function of the treatment time, were observed. A progressive increase of the specific surface area up to 28 m²/g as a consequence of the particle size reduction took place at intermediate milling times (5 h) and reduced to about 10 m²/g at prolonged milling (20 h). Even the thermo-structural behaviour of the particulate was significantly modified. For 20-h milled talc, a severe decrease of the dehydroxylation temperature from about 900–600 °C was observed with a concomitant anticipation of the recrystallisation of talc into MgSiO₃ (enstatite). The τ(ε) behaviour of the compound was strongly affected by the milling treatment changing from a shear-softening regime (untreated and 1 h) to a shear-hardening one (20 h). The observed changes of talc are of great importance to understand the rheology and the thermal transformation kinetics of talc compounds and can be exploited in those industrial applications that required milling of talc, such as in the production of talc-polymers nanocomposites or in medium–high-temperature ceramic processes.     

Controllability method for acoustic scattering with spectral elements

We formulate the Helmholtz equation as an exact controllability problem for the time-dependent wave equation. The problem is then discretized in time domain with central finite difference scheme and in space domain with spectral elements. This approach leads to high accuracy in spatial discretization. Moreover, the spectral element method results in diagonal mass matrices, which makes the time integration of the wave equation highly efficient. After discretization, the exact controllability problem is reformulated as a least-squares problem, which is solved by the conjugate gradient method. We illustrate the method with some numerical experiments, which demonstrate the significant improvements in efficiency due to the higher order spectral elements. For a given accuracy, the controllability technique with spectral element method requires fewer computational operations than with conventional finite element method. In addition, by using higher order polynomial basis the influence of the pollution effect is reduced.