Evidence of variable H-bond network for nitroxide radicals in protic solvents

This letter presents the results of a thorough computational investigation of two prototypical nitroxide spin probes in two different protic solvents, namely water and methanol, based on the combined use of Car-Parrinello molecular dynamic simulations and static cluster/continuum quantum chemical computations. Remarkable changes in solvation networks were found on going from aqueous to methanolic solutions. Moreover, despite their structural similarity, the two nitroxide probes display quite different behaviors in water. This provides a rationalization of indirect experimentally available indications. Eventually, the combination of static and dynamical ab initio methods exploited in the present study allows to dissect many subtle features of the nitroxide-solvent interaction, and also allows for an analysis of solvent effects on magnetic parameters (hyperfine coupling constants and g-tensor shift).     

Dark Energy from Entanglement Entropy

We show that quantum decoherence, in the context of observational cosmology, can be connected to the cosmic dark energy. The decoherence signature could be characterized by the existence of quantum entanglement between cosmological eras. As a consequence, the Von Neumann entropy related to the entanglement process, can be compared to the thermodynamical entropy in a homogeneous and isotropic universe. The corresponding cosmological models are compatible with the current observational bounds being able to reproduce viable equations of state without introducing a priori any cosmological constant. In doing so, we investigate two cases, corresponding to two suitable cosmic volumes, V∝a ³ and V∝H ^?3, and find two models which fairly well approximate the current cosmic speed up. The existence of dark energy can be therefore reinterpreted as a quantum signature of entanglement, showing that the cosmological constant represents a limiting case of a more complicated model derived from the quantum decoherence.     

Colour diversification in octocorals based on conjugated polyenes: A Raman spectroscopic view

Polyenic pigments in octocorals have been investigated by Raman spectroscopy using laser excitation at 532, 785 and 1064 nm. The spectral features suggest the structural nature of carotenoids from Phyllogorgia dilatata, Leptogorgia punicea, Muricea atlantica, Carijoa riisei and conjugated polyenals from L. punicea, L. setacea, Muricea flamma and Renilla muelleri. The observed vibrational bands at ca. 1540–1520 ν₁(C=C), 1159 ν₂(C–C) and 1005 cm⁻¹ ρ₃(C–CH₃) were assigned to carotenoids, whereas the identification of non‐methylated conjugated polyenals have been proposed due to two major Raman bands at ca. 1500 and 1120 cm^‐1, assigned to ν(C=C) and ν(C–C), respectively. Copyright © 2012 John Wiley & Sons, Ltd.     

Convergence properties of the supercell approach in the study of local defects in solids

The “supercell” scheme is applied to the study of local defects in MgO (Ca substitution, cation and anion vacancies) and bulk silicon (carbon substitution). The trend of the quantities of interest (defect formation energy, geometrical relaxation, charge distribution around the defect) as a function of the supercell size is explored; when neutral defects are considered, supercells containing 50 to 100 atoms are large enough to allow for most of the nuclear and electronic relaxation and to produce a negligible interaction between defects in different cells. These conclusions apply both to ionic and covalent host crystals. Present day ab initio quantum mechanical periodic computer programs can handle cells of such a size at a relatively low cost and high numerical accuracy.

When charged defects are considered (vacancies in MgO), the supercell scheme must be modified in order to avoid Coulomb divergencies, but the usually adopted correction, which consists in introducing a compensating uniform background of charge, generates spurious higher order electrostatic interactions, which are far from being negligible. The resulting defect formation energies show very slow, if any, convergence trends and “a posteriori” semiclassical corrections proposed in the literature do not represent a general solution to the problem. On the other hand, other properties, such as atom relaxation and charge distribution, show a much faster convergence than energy with respect to the cell size.     

Cosmological dark energy effects from entanglement

The thorny issue of relating information theory to cosmology is here addressed by assuming a possible connection between quantum entanglement measures and observable universe. In particular, we propose a cosmological toy model, where the equation of state of the cosmological fluid, which drives the today observed cosmic acceleration, can be inferred from quantum entanglement between different cosmological epochs. In such a way the dynamical dark energy results as byproduct of quantum entanglement.     

Probing quantum-vacuum geometrical effects with cold atoms

The lateral Casimir-Polder force between an atom and a corrugated surface should allow one to study experimentally nontrivial geometrical effects in the electromagnetic quantum vacuum. Here, we derive the theoretical expression of this force in the scattering approach. We show that large corrections to the "proximity force approximation" could be measured using present-day technology with a Bose-Einstein condensate used as a vacuum field sensor.     

Critical role of laser wavelength on carbon films grown by PLD of graphite

The structure of thin films deposited by pulsed laser ablation (PLD) is strongly dependent on experimental conditions, like laser wavelength and fluence, substrate temperature and pressure. Depending on these parameters we obtained various kinds of carbon materials varying from dense, mainly tetrahedral amorphous carbon (ta-C), to less compact vertically oriented graphene nano-particles. Thin carbon films were grown by PLD on n-Si 〈100〉 substrates, at temperatures ranging from RT to 800°C, from a rotating graphite target operating in vacuum. The laser ablation of the graphite target was performed by a UV pulsed ArF excimer laser (λ=193 nm) and a pulsed Nd:YAG laser, operating in the near IR (λ=1064 nm). The film structure and texturing, characterised by X-ray diffraction analysis, performed at grazing incidence (GI-XRD), and the film density, evaluated by X-ray reflectivity measurements, are strongly affected both by laser wavelength and fluence and by substrate temperature. Micro-Raman and GI-XRD analysis established the progressive formation of aromatic clusters and cluster condensation into vertically oriented nano-sized graphene structures as a direct function of increasing laser wavelength and deposition temperature. The film density, negatively affected by substrate temperature and laser wavelength and fluence, in turn, results in a porous bulk configuration and a high macroscopic surface roughness as shown by SEM characterisation. These structural property modifications induce a relevant variation also on the emission properties of carbon nano-structures, as evidenced by field emission measurements. This work is dedicated to our friend Giorgio who passed away 20th August.     

Unravelling the Phytochemical Composition and the Pharmacological Properties of an Optimized Extract from the Fruit from Prunus mahaleb L.: From Traditional Liqueur Market to the Pharmacy Shelf

Prunus mahaleb L. fruit has long been used in the production of traditional liqueurs. The fruit also displayed scavenging and reducing activity, in vitro. The present study focused on unravelling peripheral and central protective effects, antimicrobial but also anti-COVID-19 properties exerted by the water extract of P. mahaleb. Anti-inflammatory effects were studied in isolated mouse colons exposed to lipopolysaccharide. Neuroprotection, measured as a blunting effect on hydrogen-peroxide-induced dopamine turnover, was investigated in hypothalamic HypoE22 cells. Antimicrobial effects were tested against different Gram+ and Gram- bacterial strains. Whereas anti-COVID-19 activity was studied in lung adenocarcinoma H1299 cells, where the gene expression of ACE2 and TMPRSS2 was measured after extract treatment. The bacteriostatic effects induced on Gram+ and Gram- strains, together with the inhibition of COX-2, TNFα, HIF1α, and VEGFA in the colon, suggest the potential of P. mahaleb water extract in contrasting the clinical symptoms related to ulcerative colitis. The inhibition of the hydrogen peroxide-induced DOPAC/DA ratio indicates promising neuroprotective effects. Finally, the downregulation of the gene expression of ACE2 and TMPRSS2 in H1299 cells, suggests the potential to inhibit SARS-CoV-2 virus entry in the human host. Overall, the results support the valorization of the local cultivation of P. mahaleb.     

A real-time,fluorescence-based assay for Rho-associated protein kinase activity

Inhibitors of Rho-associated protein kinase (ROCK) enzymatic activity have been shown to reduce the invasive phenotype observed in metastatic hepatocellular carcinoma (HCC). We describe the design, synthesis, and evaluation of a direct probe for ROCK activity utilizing a phosphorylation-sensitive sulfonamido-oxine fluorophore, termed Sox. The Sox fluorophore undergoes an increase in fluorescence upon phosphorylation of a proximal amino acid via chelation-enhanced fluorescence (CHEF, ex. = 360 nm and em. = 485 nm), allowing for the direct visualization of the rate of phosphate addition to a peptide substrate over time. Our optimal probe design, ROCK-S1, is capable of sensitively reporting ROCK activity with a limit of detection of 10 pM and a high degree of reproducibility (Z’-factor = 0.6 at 100 pM ROCK2). As a proof-of-principle for high-throughput screening (HTS) we demonstrate the ability to rapidly assess the efficacy of a 78 member, small molecule library against ROCK2 using a robotics platform. We identify two previously unreported ROCK2 inhibitor scaffolds, PHA665752 and IKK16, with IC₅₀ values of 3.6 μM and 247 nM respectively. Lastly, we define conditions for selectively monitoring ROCK activity in the presence of potential off-target enzymes (PKCα, PKA, and PAK) with similar substrate specificities.     

Spectral theory approach for a class of radial indefinite variational problems

Considering the radial nonlinear Schrödinger equation

($P_r$)$?\mathrm{\Delta }u+V(x)u=g(x,u)\text{in}{\mathbb{R}}^N,N\ge 3$

we aim to find a radial nontrivial solution for it, where V changes sign ensuring problem ($P_r$) is indefinite and g is an asymptotically linear nonlinearity. We work with variational methods associating problem ($P_r$) to an indefinite functional in order to apply our Abstract Linking Theorem for Cerami sequences in [8] to get a non-trivial critical point for this functional. Our goal is to make use of spectral properties of operator $A:=\mathrm{\Delta }+V(x)$ restricted to $H_{rad}^1({\mathbb{R}}^N)$, the space of radially symmetric functions in $H^1({\mathbb{R}}^N)$, for obtaining a linking geometry structure to the problem and by means of special properties of radially symmetric functions get the necessary compactness.