Semiempirical Potential in Kinetics Calculations on the HC3N + CN Reaction

The reaction between the cyano radical CN and cyanoacetylene molecule HC3N is of great interest in different astronomical fields, from star-forming regions to planetary atmospheres. In this work, we present a new synergistic theoretical approach for the derivation of the rate coefficient for gas phase neutral-neutral reactions. Statistic RRKM calculations on the Potential Energy Surface are coupled with a semiempirical analysis of the initial bimolecular interaction. The value of the rate coefficient for the HC3N + CN → H + NCCCCN reaction obtained with this method is compared with previous theoretical and experimental investigations, showing strengths and weaknesses of the new presented approach.     

PLA Nanofibers for Microenvironmental-Responsive Quercetin Release in Local Periodontal Treatment

The management of periodontitis remains a vital clinical challenge due to the interplay between the microorganisms of the dental biofilm and the host inflammatory response leading to a degenerative process in the surrounding tissues. Quercetin (QUE), a natural flavonol found in many foods, including apples, onions and tea, has exhibited prolonged and strong antibiofilm and anti-inflammatory effects both in vitro and in vivo. However, its clinical application is limited by its poor stability and water solubility, as well as its low bioavailability. Thus, in the present study, electrospun polylactic acid (PLA) nanofibers loaded with different amounts (5–10% w/w) of QUE were produced to rapidly respond to the acidic microenvironment typical of periodontal pockets during periodontal disease. This strategy demonstrated that PLA-QUE membranes can act as a drug reservoir releasing high QUE concentrations in the presence of oral bacterial infection (pH < 5.5), and thus limiting Pseudomonas aeruginosa PAO1 and Streptococcus mutans biofilm maturation. In addition, released QUE exerts antioxidant and anti-inflammatory effects on P. gingivalis Lipopolysaccharide (LPS)-stimulated human gingival fibroblast (HGFs). The reported results confirmed that PLA-QUE membranes could inhibit subgingival biofilm maturation while reducing interleukin release, thereby limiting host inflammatory response. Overall, this study provided an effective pH-sensitive drug delivery system as a promising strategy for treating periodontitis.     

Effect of Tomato Peel Extract Grown under Drought Stress Condition in a Sarcopenia Model

Tomatoes and their derivates represent an important source of natural biologically active components. The present study aims to investigate the protective effect of tomato peel extracts, grown in normal (RED-Ctr) or in drought stress (RED-Ds) conditions, on an experimental model of sarcopenia. The phenolic profile and total polyphenols content (TPC) of RED-Ctr and RED-Ds were determined by Ultra High-Performance Liquid Chromatography (UHPLC) analyses coupled to electrospray ionization high-resolution mass spectrometry (ESI-HR-MS). Human skeletal muscle myoblasts (HSMM) were differentiated in myotubes, and sarcopenia was induced by dexamethasone (DEXA) treatment. Differentiation and sarcopenia were evaluated by both real-time PCR and immunofluorescent techniques. Data show that myosin heavy chain 2 (MYH2), troponin T (TNNT1), and miogenin (MYOG) were expressed in differentiated myotubes. 5 μg Gallic Acid Equivalent (GAE/mL) of TPC from RED-Ds extract significantly reduced muscle atrophy induced by DEXA. Moreover, Forkhead BoxO1 (FOXO1) expression, involved in cell atrophy, was significantly decreased by RED-Ds extract. The protective effect of tomato peel extracts depended on their qualitative polyphenolic composition, resulting effectively in the in vitro model of sarcopenia.     

Anti-Staphylococcal Activity of the Auranofin Analogue Bearing Acetylcysteine in Place of the Thiosugar: An Experimental and Theoretical Investigation

Auranofin (AF, hereafter) is an orally administered chrysotherapeutic agent approved for the treatment of rheumatoid arthritis that is being repurposed for various indications including bacterial infections. Its likely mode of action involves the impairment of the TrxR system through the binding of the pharmacophoric cation [AuPEt₃]⁺. Accordingly, a reliable strategy to expand the medicinal profile of AF is the replacement of the thiosugar moiety with different ligands. Herein, we aimed to prepare the AF analogue bearing the acetylcysteine ligand (AF-AcCys, hereafter) and characterize its anti-staphylococcal activity. Biological studies revealed that AF-AcCys retains an antibacterial effect superimposable with that of AF against Staphylococcus aureus, whereas it is about 20 times less effective against Staphylococcus epidermidis. Bioinorganic studies confirmed that upon incubation with human serum albumin, AF-AcCys, similarly to AF, induced protein metalation through the [AuPEt₃]⁺ fragment. Additionally, AF-AcCys appeared capable of binding the dodecapeptide Ac-SGGDILQSGCUG-NH₂, corresponding to the tryptic C-terminal fragment (488–499) of hTrxR. To shed light on the pharmacological differences between AF and AF-AcCys, we carried out a comparative experimental stability study and a theoretical estimation of bond dissociation energies, unveiling the higher strength of the Au–S bond in AF-AcCys. From the results, it emerged that the lower lipophilicity of AF-AcCys with respect to AF could be a key feature for its different antibacterial activity. The differences and similarities between AF and AF-AcCys are discussed, alongside the opportunities and consequences that chemical structure modifications imply.     

Ising transition in the two-dimensional quantum J1-J2 Heisenberg model

We study the thermodynamics of the spin-S two-dimensional quantum Heisenberg antiferromagnet on the square lattice with nearest (J1) and next-nearest (J2) neighbor couplings in its collinear phase (J(2)/J(1)>0.5), using the pure-quantum self-consistent harmonic approximation. Our results show the persistence of a finite-temperature Ising phase transition for every value of the spin, provided that the ratio J(2)/J(1) is greater than a critical value corresponding to the onset of collinear long-range order at zero temperature. We also calculate the spin and temperature dependence of the collinear susceptibility and correlation length, and we discuss our results in light of the experiments on Li2VOSiO4 and related compounds.     

Constraining extended theories of gravity using Solar System tests

Solar System tests give nowadays constraints on the estimated value of the cosmological constant, which can be accurately derived from different experiments regarding gravitational redshift, light deflection, gravitational time-delay and geodesic precession. Assuming that each reasonable theory of gravitation should satisfy Solar System tests, we use these limits on the estimated value of the cosmological constant to constrain extended theories of Gravity, which are nowadays studied as possible theories for cosmological models and provide viable solutions to the cosmological constant problem and the explanation of the present acceleration of the Universe. We obtain that the estimated values, from Solar System tests, for the parameters appearing in the extended theories of Gravity are orders of magnitude bigger than the values obtained in the framework of cosmologically relevant theories.     

Modeling the phase diagram of carbon

We determined the phase diagram involving diamond, graphite, and liquid carbon using a recently developed semiempirical potential. Using accurate free-energy calculations, we computed the solid-solid and solid-liquid phase boundaries for pressures and temperatures up to 400 GPa and 12 000 K, respectively. The graphite-diamond transition line that we computed is in good agreement with experimental data, confirming the accuracy of the employed empirical potential. On the basis of the computed slope of the graphite melting line, we rule out the hotly debated liquid-liquid phase transition of carbon. Our simulations allow us to give accurate estimates of the location of the diamond melting curve and of the graphite-diamond-liquid triple point.     

Multiple periodic solutions of scalar second order differential equations

We prove multiplicity of periodic solutions for a scalar second order differential equation with an asymmetric nonlinearity, thus generalizing previous results by Lazer and McKenna (1987) [1] and Del Pino, Manasevich and Murua (1992) [2]. The main improvement lies in the fact that we do not require any differentiability condition on the nonlinearity. The proof is based on the use of the Poincaré-Birkhoff Fixed Point Theorem.     

Atomic intersection of σ-fields and some of its consequences

Let ${(\Omega, \mathcal{F}, P)}$ be a probability space. For each ${\mathcal{G}\subset\mathcal{F}}$ , define ${\overline{\mathcal{G}}}$ as the σ-field generated by ${\mathcal{G}}$ and those sets ${F\in \mathcal{F}}$ satisfying ${P(F)\in\{0,1\}}$ . Conditions for P to be atomic on ${\cap_{i=1}^k\overline{\mathcal{A}_i}}$ , with ${\mathcal{A }_1,\ldots,\mathcal{A}_k\subset\mathcal{F}}$ sub-σ-fields, are given. Conditions for P to be 0-1-valued on ${\cap_{i=1}^k \overline{\mathcal{A}_i}}$ are given as well. These conditions are useful in various fields, including Gibbs sampling, iterated conditional expectations and the intersection property.