Thermodynamics of multi-horizon spacetimes

General Relativity and Gravitation -     

S‐Nitrosoglutathione‐Based Nitric Oxide‐Releasing Nanofibers Exhibit Dual Antimicrobial and Antithrombotic Activity for Biomedical Applications

The novel use of nanofibers as a physical barrier between blood and medical devices has allowed for modifiable, innovative surface coatings on devices ordinarily plagued by thrombosis, delayed healing, and chronic infection. In this study, the nitric oxide (NO) donor S‐nitrosoglutathione (GSNO) is blended with the biodegradable polymers polyhydroxybutyrate (PHB) and polylactic acid (PLA) for the fabrication of hemocompatible, antibacterial nanofibers tailored for blood‐contacting applications. Stress/strain behavior of different concentrations of PHB and PLA is recorded to optimize the mechanical properties of the nanofibers. Nanofibers incorporated with different concentrations of GSNO (10, 15, 20 wt%) are evaluated based on their NO‐releasing kinetics. PLA/PHB + 20 wt% GSNO nanofibers display the greatest NO release over 72 h (0.4–1.5 × 10^?10 mol mg^?1 min^?1). NO‐releasing fibers successfully reduce viable adhered bacterial counts by ≈80% after 24 h of exposure to Staphylococcus aureus. NO‐releasing nanofibers exposed to porcine plasma reduce platelet adhesion by 64.6% compared to control nanofibers. The nanofibers are found noncytotoxic (>95% viability) toward NIH/3T3 mouse fibroblasts, and 4′,6‐diamidino‐2‐phenylindole and phalloidin staining shows that fibroblasts cultured on NO‐releasing fibers have improved cellular adhesion and functionality. Therefore, these novel NO‐releasing nanofibers provide a safe antimicrobial and hemocompatible coating for blood‐contacting medical devices.     

Correction to: Macrocycles in dual role: ancillary ligands in metal complexes and organocatalysts for the ring‑opening polymerization of lactide

Journal of Inclusion Phenomena and Macrocyclic Chemistry - A correction to this paper has been published: https://doi.org/10.1007/s10847-021-01060-y     

Multi-C−C/C−N-Coupled Light-Emitting Aliphatic Terpolymers: N−H-Functionalized Fluorophore Monomers and High-Performance Applications

To circumvent costly fluorescent labeling, five nonconventional, multifunctional, intrinsically fluorescent aliphatic terpolymers ( 1 – 5 ) have been synthesized by C−C/C−N-coupled, solution polymerization of two non-emissive monomers with protrusions of fluorophore monomers generated in situ. These scalable terpolymers were suitable for sensing and high-performance exclusion of Cu^II, logic function, and bioimaging. The structures of the terpolymers, in situ attachment of fluorescent monomers, aggregation-induced enhanced emission, bioimaging ability, and super adsorption were investigated by ¹H and ¹³C NMR, EPR, FTIR, X-ray photoelectron, UV/Vis, and atomic absorption spectroscopy, thermogravimetric analysis, high-resolution transmission electron microscopy, dynamic light scattering, solid-state fluorescence, fluorescence imaging, and fluorescence lifetime measurements, as well as by isotherm, kinetics, and thermodynamic studies. The geometries and electronic structures of the fluorophores and the absorption and emission properties of the terpolymers were examined by DFT, time-dependent DFT, and natural transition orbital analyses. For 1 , 2 , and 5 , the limits of detection were determined to be 1.03×10⁻⁷, 1.65×10⁻⁷, and 1.77×10⁻⁷ m , respectively, and the maximum adsorption capacities are 1575.21, 1433.70, and 1472.21 mg g⁻¹, respectively.     

Electrochemistry and Spin-Crossover Behavior of Fluorinated Terpyridine-Based Co(II) and Fe(II) Complexes

Due to their ability to form stable molecular complexes that have tailor-made properties, terpyridine ligands are of great interest in chemistry and material science. In this regard, we prepared two terpyridine ligands with two different fluorinated phenyl rings on the backbone. The corresponding Co^II and Fe^II complexes were synthesized and characterized by single-crystal X-ray structural analysis, electrochemistry and temperature-dependent SQUID magnetometry. Single crystal X-ray diffraction analyses at 100 K of these complexes revealed Co−N and Fe−N bond lengths that are typical of low spin Co^II and Fe^II centers. The metal centers are coordinated in an octahedral fashion and the fluorinated phenyl rings on the backbone are twisted out of the plane of the terpyridine unit. The complexes were investigated with cyclic voltammetry and UV/Vis-NIR spectroelectrochemistry. All complexes show a reversible oxidation and several reduction processes. Temperature dependent SQUID magnetometry revealed a gradual thermal SCO behavior in two of the complexes, while EPR spectroscopy provided further insights on the electronic structure of the metal complexes, as well as site of reduction.     

Palladium‐Catalyzed C?H Activation of N‐Allyl Imines: Regioselective Allylic Alkylations to Deliver Substituted Aza‐1,3‐Dienes

A new mode of activation of an imine via a rare aza‐substituted π‐allyl complex is described. Palladium‐catalyzed C(sp³) H activation of the N‐allyl imine and the subsequent nucleophilic attack by the α‐alkyl cyanoester produced the 1‐aza‐1,3‐diene as the sole regioisomer. In contrast, nucleophilic attack by the α‐aryl cyanoester exclusively delivered the 2‐aza‐1,3‐diene, which was employed in an inverse‐electron‐demand Diels–Alder reaction for heterobiaryl synthesis.     

Large amplitude free flexural vibrations of laminated composite skew plates

Here, the large amplitude free flexural vibration behaviors of thin laminated composite skew plates are investigated using finite element approach. The formulation includes the effects of shear deformation, in-plane and rotary inertia. The geometric non-linearity based on von Karman's assumptions is introduced. The non-linear governing equations obtained employing Lagrange's equations of motion are solved using the direct iteration technique. The variation of non-linear frequency ratios with amplitudes is brought out considering different parameters such as skew angle, number of layers, fiber orientation, boundary condition and aspect ratio. The influence of higher vibration modes on the non-linear dynamic behavior of laminated skew plates is also highlighted. The present study reveals the redistribution of vibrating mode shape at certain amplitude of vibration depending on geometric and lamination parameters of the plate. Also, the degree of hardening behavior increases with the skew angle and its rate of change depends on the level of amplitude of vibration.     

Stagnation-point flow of a viscoelastic fluid towards a stretching surface

An analysis is made of the steady two-dimensional stagnation-point flow of an incompressible viscoelastic fluid over a flat deformable surface when the surface is stretched in its own plane with a velocity proportional to the distance from the stagnation-point. It is shown that for a viscoelastic fluid of short memory (obeying Walters’ B′ model), a boundary layer is formed when the stretching velocity of the surface is less than the inviscid free-stream velocity and velocity at a point increases with increase in the elasticity of the fluid. On the other hand, an inverted boundary layer is formed when the surface stretching velocity exceeds the velocity of the free stream and the velocity decreases with increase in the elasticity of the fluid. A novel result of the analysis is that the flow near the stretching surface is that corresponding to an inviscid stagnation-point flow when the surface stretching velocity is equal to the velocity of the free stream. Temperature distribution in the boundary layer is found when the surface is held at constant temperature and surface heat flux is determined. It is found that temperature at a point decreases with increase in the elasticity of the fluid.     

Nonlinear finite element analysis of laminated composite spherical shell vibration under uniform thermal loading

In this article, nonlinear free vibration behavior of laminated composite shallow shell under uniform temperature load is investigated. The mid-plane kinematics of the laminated shell is evaluated based on higher order shear deformation theory to count the out of plane shear stresses and strains accurately. The nonlinearity in geometry is taken in Green-Lagrange sense due to the thermal load. In addition to that, all the nonlinear higher order terms are taken in the mathematical model to capture the original flexure of laminated panel. A nonlinear finite element model is proposed to discretise the developed model and the governing equations are derived using Hamilton’s principle. The sets of governing equations are solved using a direct iterative method. In order to validate the model, the results are compared with the available published literature and the limitations of the existing models have been discussed. Finally, some numerical experimentation has been done using the developed nonlinear model for different parameters (thickness ratio, curvature ratio, modular ratio, support condition, lamination scheme, amplitude ratio and thermal expansion coefficient) and their effects on the responses are discussed in detail.