Nonlocal integral elasticity in nanostructures,mixtures, boundary effects and limit behaviours

Nonlocal elasticity is addressed in terms of integral convolutions for structural models of any dimension, that is bars, beams, plates, shells and 3D continua. A characteristic feature of the treatment is the recourse to the theory of generalised functions (distributions) to provide a unified presentation of previous proposals. Local-nonlocal mixtures are also included in the analysis. Boundary effects of convolutions on bounded domains are investigated, and analytical evaluations are provided in the general case. Methods for compensation of boundary effects are compared and discussed with a comprehensive treatment. Estimates of limit behaviours for extreme values of the nonlocal parameter are shown to give helpful information on model properties, allowing for new comments on previous proposals. Strain-driven and stress-driven models are shown to emerge by swapping the mechanical role of input and output fields in the constitutive convolution, with stress-driven elastic model leading to well-posed problems. Computations of stress-driven nonlocal one-dimensional elastic models are performed to exemplify the theoretical results.     

Self‐assembling amphiphilic block copolymer from renewable δ‐decalactone and δ‐dodecalactone

Aliphatic polyesters have many applications in the biomedical field due to their properties and facile degradation. They are commonly synthesized via ring opening polymerization (ROP) with metal‐based catalysts, but as high temperatures are needed and the products contain metal, organocatalysts are now widely adopted to polymerize them at room temperature while also ensuring short reaction times. Here, 1,7,7‐triazabicyclo[4.4.0]‐dec‐5‐ene is used to polymerize less reactive but renewably‐derived lactones, namely δ‐decalactone and δ‐dodecalactone. These monomers were chosen in the attempt of creating renewable and highly lipophilic materials for drug delivery applications as alternatives to the more traditional, but non‐renewable δ‐valerolactone and ?‐caprolactone. A combination of ROP and living radical polymerization Reversible Addition‐Fragmentation Chain Transfer is proposed here to synthesize grafted block copolymers. They are able to self‐assemble in water, forming micelles where the lipophilic polyester core is able to entrap a lipophilic drug, thus making the system a good candidate for drug delivery. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3788–3797     

Synthesis of 2′‐Deoxy‐1′‐homo‐N‐nucleosides with Anti‐Influenza Activity by Catalytic Methyltrioxorhenium (MTO)/H2O2 Oxyfunctionalization

This paper describes a new route for the synthesis of 1′‐homo‐N‐nucleoside derivatives by means of either methyltrioxorhenium (MTO) or supported MTO catalysts, with H₂O₂ as the primary oxidant. Under these selective conditions, the oxyfunctionalization of the heterocyclic ring and the N heteroatom oxidation were operative processes, regardless of the type of substrate used, that is, purine or pyrimidine derivatives. In addition, the oxidation of 1′‐homo‐N‐thionucleosides, showed the occurrence of site‐specific oxidative nucleophilic substitutions of the heterocyclic ring. The MTO/H₂O₂ system showed, in general, high reactivity under both homogeneous and heterogeneous conditions, affording the final products with high conversion values of substrates and from medium to high yields. Many of the novel 1′‐homo‐N‐nucleoside analogues were active against the influenza A virus, without any cytotoxic effects, retaining their activity in both protected and unprotected forms.     

Phospholipid-based nonlamellar mesophases for delivery systems: Bridging the gap between empirical and rational design

Phospholipids are ubiquitous cell membrane components and relatively well-accepted ingredients due to their natural origin. Phosphatidylcholine (PC) in particular offers a promising alternative to monoglycerides for lyotropic liquid crystalline (LLC) delivery system applications in the food, cosmetics and pharmaceutical industries, provided its strong tendency to form zero-mean curvature lamellar mesophases in water can be overcome. Higher negative curvatures are usually reached through the addition of a third lipid component, forming a ternary diagram phospholipid/water/oil.     

Sub-persistence-length complex scaling behavior in lysozyme amyloid fibrils

We combine atomic force microscopy single-molecule analysis with polymer physics concepts to study molecular conformations of lysozyme amyloid fibrils. We resolve a wavy structure of the fibrils in which the scaling behavior varies at multiple length scales. Bond and pair correlation functions, end-to-end distribution, and wormlike chain model identify three characteristic length scales. At short length scales (≈150 nm), there is a first bending transition of the fibrils corresponding to a bending length L(b). At larger length scales (>2L(b)), fibrils become pseudoperiodic and start to undulate. Finally, at length scales larger than the persistence length (~ μm), the fibrils become flexible and follow a 2D self-avoiding random walk. We interpret these results in terms of the twisting of the fibrils and the impact this has on the area moment of inertia and the propensity of the fibril to bend.     

Efficient visible-light photocatalytic water splitting by minute amounts of gold supported on nanoparticulate CeO2 obtained by a biopolymer templating method

When irradiated with visible light (λ > 400 nm) 1 wt % gold-supported ceria nanoparticles generate oxygen from water (10.5 μmol·h(-1)) more efficiently than the standard WO(3) (1.7 μmol·h(-1)) even under UV irradiation (9.5 μmol·h(-1)). This remarkable photocatalytic activity arises from a novel preparation method to reduce the particle size of ceria (5 nm) by means of electrostatic binding of Ce(4+) to alginate gel, subsequent supercritical CO(2) drying, and calcination. The low loading of Au is crucial for the observed high catalytic activity.     

Approximate calculation of the matrix elements of Coulomb and exchange operators for the “core” electrons of the atoms K through Zn

A method which allows to approximate the Coulomb and exchange integrals employed in valence-electron-only SCF calculations with a few parameters, as described in a previous paper, is extended to the atoms from K to Zn. All the necessary parameters for these atoms are given. Extension to other atoms is in progress.