A theoretical and matrix-isolation FT-IR investigation of the conformational landscape of N-acetylcysteine

The conformational landscape of N-acetylcysteine (NAC) has been investigated by a combined experimental matrix-isolation FT-IR and theoretical methodology. This combination is a powerful tool to study the conformational behavior of relatively small molecules. Geometry optimizations at the HF/3-21 level resulted in 438 different geometries with an energy difference smaller than 22 kJ mol⁻¹. Among these, six conformations were detected with a relative energy difference smaller than 10 kJ mol⁻¹ at the DFT(B3LYP)/6-31++G∗∗ level of theory. These were finally subjected to MP2/6-31++G∗∗ optimizations which resulted in five minima. The vibrational and thermodynamical properties of these conformations were calculated at both the DFT and MP2 methodologies. Experimentally NAC was isolated in an argon matrix at 16 K after being sublimated at 323 K. The most stable MP2 form appeared to be dominant in the experimental spectra but the presence of three other conformations with ΔE_MP2 < 10 kJ mol⁻¹ was also demonstrated. The experimentally observed abundance of the H-bond containing conformations appeared to be in good accordance with the predicted MP2 value.     

Moser-type inequalities in Lorentz spaces

Moser-type estimates for functions whose gradient is in the Lorentz space L(n, q), 1q, are given. Similar results are obtained for solutions uH _inf0 ^sup1 of Au=(f _i ) _{x i} , where A is a linear elliptic second order differential operator and |f|L(n, q), 2q.Work partially supported by MURST (40%).     

Ionic liquid confined in silica nanopores: molecular dynamics in the isobaric–isothermal ensemble

Molecular dynamics simulations in the isobaric–isothermal ensemble are used to investigate the structure and dynamics of an ionic liquid confined at ambient temperature and pressure in hydroxylated amorphous silica nanopores. The use of the isobaric–isothermal ensemble allows estimating the effect of confinement and surface chemistry on the density of the confined ionic liquid. The structure of the confined ionic liquid is investigated using density profiles and structural order parameters while its dynamics is assessed by determining the mobility and ionic conductivity of the confined phase. Despite the important screening of the electrostatic interactions (owing to the small Debye length in ionic liquids), the local structure of the confined ionic liquid is found to be mostly driven by electrostatic interactions. We show that both the structure and dynamics of the confined ionic liquid can be described as the sum of a surface contribution arising from the ions in contact with the surface and a bulk-like contribution arising from the ions located in the pore centre; as a result, most properties of the confined ionic liquid are a simple function of the surface-to-volume ratio of the host porous material. In contrast, the ionic conductivity of the confined ionic liquid, which is a collective dynamical property, is found to be similar to the bulk. This study sheds light on the complex behaviour of hybrid materials made up of ionic liquid confined in inorganic porous materials.     

Unit Tangent Sphere Bundles and Two-Point Homogeneous Spaces

We characterize two-point homogeneous spaces, locally symmetric spaces, C and B-spaces via properties of the standard contact metric structure of their unit tangent sphere bundle. Further, under various conditions on a Riemannian manifold, we show that its unit tangent sphere bundle is a (locally) homogeneous contact metric space if and only if the manifold itself is (locally) isometric to a two-point homogeneous space.     

Coordination games on graphs

We introduce natural strategic games on graphs, which capture the idea of coordination in a local setting. We study the existence of equilibria that are resilient to coalitional deviations of unbounded and bounded size (i.e., strong equilibria and k-equilibria respectively). We show that pure Nash equilibria and 2-equilibria exist, and give an example in which no 3-equilibrium exists. Moreover, we prove that strong equilibria exist for various special cases. We also study the price of anarchy (PoA) and price of stability (PoS) for these solution concepts. We show that the PoS for strong equilibria is 1 in almost all of the special cases for which we have proven strong equilibria to exist. The PoA for pure Nash equilbria turns out to be unbounded, even when we fix the graph on which the coordination game is to be played. For the PoA for k-equilibria, we show that the price of anarchy is between \(2(n-1)/(k-1) - 1\) and \(2(n-1)/(k-1)\). The latter upper bound is tight for \(k=n\) (i.e., strong equilibria). Finally, we consider the problems of computing strong equilibria and of determining whether a joint strategy is a k-equilibrium or strong equilibrium. We prove that, given a coordination game, a joint strategy s, and a number k as input, it is co-NP complete to determine whether s is a k-equilibrium. On the positive side, we give polynomial time algorithms to compute strong equilibria for various special cases.     

One-loop effective action for non-local modified Gauss–Bonnet gravity in de Sitter space

We discuss the classical and quantum properties of non-local modified Gauss–Bonnet gravity in de Sitter space, using its equivalent representation via string-inspired local scalar-Gauss–Bonnet gravity with a scalar potential. A classical, multiple de Sitter universe solution is found where one of the de Sitter phases corresponds to the primordial inflationary epoch, while the other de Sitter space solution—the one with the smallest Hubble rate—describes the late-time acceleration of our universe. A Chameleon scenario for the theory under investigation is developed, and it is successfully used to show that the theory complies with gravitational tests. An explicit expression for the one-loop effective action for this non-local modified Gauss–Bonnet gravity in the de Sitter space is obtained. It is argued that this effective action might be an important step towards the solution of the cosmological constant problem.     

Kinetic Formulation and Uniqueness for Scalar Conservation Laws with Discontinuous Flux

We prove a uniqueness result for BV solutions of scalar conservation laws with discontinuous flux in several space dimensions. The proof is based on the notion of kinetic solution and on a careful analysis of the entropy dissipation along the discontinuities of the flux.     

A Multi-Technique Investigation of the Complex Formation Equilibria between Bis-Deferiprone Derivatives and Oxidovanadium (IV)

The increasing biomedical interest in high-stability oxidovanadium(IV) complexes with hydroxypyridinone ligands leads us to investigate the complex formation equilibria of V^IVO²⁺ ion with a tetradentate ligand, named KC21, which contains two 3-hydroxy-1,2-dimethylpyridin-4(1H)-one (deferiprone) moieties, and with the simple bidentate ligand that constitutes the basic unit of KC21, for comparison, named L5. These equilibrium studies were conducted with joined potentiometric–spectrophotometric titrations, and the results were substantiated with EPR measurements at variable pH values. This multi-technique study gave evidence of the formation of an extremely stable 1:1 complex between KC21 and oxidovanadium(IV) at a physiological pH, which could find promising pharmacological applications.     

Coordination Cage-Based Emulsifiers: Templated Formation of Metal Oxide Microcapsules Monitored by In Situ LC-TEM

Metallo-supramolecular self-assembly has yielded a plethora of discrete nanosystems, many of which show competence in capturing guests and catalyzing chemical reactions. However, the potential of low-molecular bottom-up self-assemblies in the development of structured inorganic materials has rarely been methodically explored so far. Herein, we present a new type of metallo-supramolecular surfactant with the ability to stabilize non-aqueous emulsions for a significant period. The molecular design of the surfactant is based on a heteroleptic coordination cage ( CGA-3 ; CGA =Cage-based Gemini Amphiphile), assembled from two pairs of organic building blocks, grouped around two Pd(II) cations. Shape-complementarity between the differently functionalized components generates discrete amphiphiles with a tailor-made polarity profile, able to stabilize non-aqueous emulsions, such as hexadecane-in-DMSO. These emulsions were used as a medium for the synthesis of spherical metal oxide microcapsules (titanium oxide, zirconium oxide, and niobium oxide) from soluble, water-sensitive alkoxide precursors by allowing a controlled dosage of water to the liquid-liquid phase boundary. Synthesized materials were analyzed by a combination of electron microscopic techniques. In situ liquid cell transmission electron microscopy (LC-TEM) was utilized for the first time to visualize the dynamics of the emulsion-templated formation of hollow inorganic titanium oxide and zirconium oxide microspheres.     

Plasma modified POF sensors for in situ environmental monitoring of museum indoor environments

A cumulative sensor for in situ monitoring of H₂S vapors in museum showcases based on plastic optical fiber (POF) has been developed. H₂S is responsible for the tarnishing of silver artifacts, so monitoring their total exposure over time to sulfide rich atmospheres can help in choosing the correct display procedure and, consequently, lead to improvements in their conservation.