A Porous Gelatin Methacrylate-Based Material for 3D Cell-Laden Constructs

3D constructs are fundamental in tissue engineering and cancer modeling, generating a demand for tailored materials creating a suitable cell culture microenvironment and amenable to be bioprinted. Gelatin methacrylate (GelMA) is a well-known functionalized natural polymer with good printability and binding motifs allowing cell adhesion; however, its tight micropores induce encapsulated cells to retain a non-physiological spherical shape. To overcome this problem, blended GelMa is here blended with Pluronic F-127 (PLU) to modify the hydrogel internal porosity by inducing the formation of larger mesoscale pores. The change in porosity also leads to increased swelling and a slight decrease in Young's modulus. All blends form stable hydrogels both when cast in annular molds and bioprinted in complex structures. Embedded cells maintain high viability, and while Neuroblastoma cancer cells typically aggregate inside the mesoscale pores, Mesenchymal Stem Cells stretch in all three dimensions, forming cell–cell and cell–ECM interactions. The results of this work prove that the combination of tailored porous materials with bioprinting techniques enables to control both the micro and macro architecture of cell-laden constructs, a fundamental aspect for the development of clinically relevant in vitro constructs.     

Degradable and Recyclable Polyesters from Multiple Chain Length Bio- and Waste-Sourceable Monomers

Monomers sourced from waste or biomass are often mixtures of different chain lengths; e.g. catalytic oxidation of polyethylene waste yields mixtures of dicarboxylic acids (DCAs). Yet, polyesters synthesized from such monomer mixtures have rarely been studied. We report polyesters based on multiple linear aliphatic DCAs, present in chain length distributions that vary in their centers and ranges. We demonstrate that these materials can adopt high-density polyethylene-like solid state structures, and are ductile (e.g. E_t 610 MPa), allowing for injection molding, or film and fiber extrusion. Melting and crystallization points of the polyesters show no odd-even effects as dipoles cannot favorably align in the crystal, similar to traditional odd carbon numbered, long-chain DCA polyesters. Biodegradation studies of ¹³C-labelled polyesters in soil reveal rapid mineralization, and depolymerization by methanolysis indicates suitability for closed-loop recycling.     

Di‐μ‐hydroxo‐bis{(aceto­nitrile)dibenzyl(6‐methyl‐2‐pyridylmethyl)amine‐κ2N,N]copper(II)} bis(perchlorate)

The title compound corresponds to a copper(II) dimer, [Cu₂(OH)₂(C₂H₃N)₂(C₂₁H₂₂N₂)₂](ClO₄)₂, where the metal centres are μ₂‐bridged by hydroxo groups. The coordination of each copper(II) centre is a slightly distorted square‐based pyramid, with two N atoms from dibenzyl(6‐methyl‐2‐pyridylmethyl)amine (BiBzMePMA) and two hydroxo O atoms occupying the basal positions, and the aceto­nitrile N atom at the apical position. The dimer is centrosymmetric, with a crystallographic inversion centre midway between the two Cu atoms [Cu⋯Cu = 2.9522 (9) Å]     

A Pd/C‐CeO2 Anode Catalyst for High‐Performance Platinum‐Free Anion Exchange Membrane Fuel Cells

One of the biggest obstacles to the dissemination of fuel cells is their cost, a large part of which is due to platinum (Pt) electrocatalysts. Complete removal of Pt is a difficult if not impossible task for proton exchange membrane fuel cells (PEM‐FCs). The anion exchange membrane fuel cell (AEM‐FC) has long been proposed as a solution as non‐Pt metals may be employed. Despite this, few examples of Pt‐free AEM‐FCs have been demonstrated with modest power output. The main obstacle preventing the realization of a high power density Pt‐free AEM‐FC is sluggish hydrogen oxidation (HOR) kinetics of the anode catalyst. Here we describe a Pt‐free AEM‐FC that employs a mixed carbon‐CeO₂ supported palladium (Pd) anode catalyst that exhibits enhanced kinetics for the HOR. AEM‐FC tests run on dry H₂ and pure air show peak power densities of more than 500 mW cm^?2.     

Novel organometallic building blocks for molecular crystal engineering. Part 4. Synthesis and characterization of mono- and bis-amido derivatives of [Co(III)(eta5-C5H4COOH)2]+ and their utilization as ligands

The synthesis and structural characterization of the hexafluorophosphate salts of the substituted bis-amido molecular complexes [Co(III)(eta5-C5H4CONHC4H3N2)2]+ (1), [Co(III)(eta5-C5H4CONHCH2C5H4N)2]+ (2), [Co(III)(eta5-C5H4CON(C5H4N)2)2]+ (3), and of the amido-carboxyl complexes [Co(III)(eta5-C5H4CON(C5H4N)2)(eta5-C5H4COOH)]+ (4), and [Co(III)(eta5-C5H4CONHC2N3(C5H4N)2)(eta5-C5H4COOH)]+ (5) are reported. The pyridyl and pyrazine substituted amido ligands on the sandwich cores have been chosen because they allow both coordination to metal centres and participation in hydrogen bonding. The hydrogen bonding interactions established by the family of complexes in the solid state has been investigated. The utilization of complex 5 for the preparation of the complex of complexes[Cd(NO3)2{Co(III)(eta5-C5H4CONHC2N3(C5H4N)(C5H4NH))(eta5-C5H4COOH)}2]6+ (6) is reported as a first example of the potential of the substituted mono-and bis-amides as ligands. The isolation and structural characterization of the carbonyl chloride cation [Co(III)(eta5-C5H4COCl)2]+ (7) as its tetrachloro cobaltate anion salt is also described.     

Anticancer Activities of Marine-Derived Phenolic Compounds and Their Derivatives

Since the middle of the last century, marine organisms have been identified as producers of chemically and biologically diverse secondary metabolites which have exerted various biological activities including anticancer, anti-inflammatory, antioxidant, antimicrobial, antifouling and others. This review primarily focuses on the marine phenolic compounds and their derivatives with potent anticancer activity, isolated and/or modified in the last decade. Reports on the elucidation of their structures as well as biosynthetic studies and total synthesis are also covered. Presented phenolic compounds inhibited cancer cells proliferation or migration, at sub-micromolar or nanomolar concentrations (lamellarins D (37), M (38), K (39), aspergiolide B (41), fradimycin B (62), makulavamine J (66), mayamycin (69), N-acetyl-N-demethylmayamycin (70) or norhierridin B (75)). In addition, they exhibited anticancer properties by a diverse biological mechanism including induction of apoptosis or inhibition of cell migration and invasive potential. Finally, phlorotannins 1–7 and bromophenols 12–29 represent the most researched phenolic compounds, of which the former are recognized as protective agents against UVB or gamma radiation-induced skin damages. Finally, phenolic metabolites were assorted into six main classes: phlorotannins, bromophenols, flavonoids, coumarins, terpenophenolics, quinones and hydroquinones. The derivatives that could not be attributed to any of the above-mentioned classes were grouped in a separate class named miscellaneous compounds.     

Deformation and failure kinetics of iPP polymorphs

In this study, the mechanical performance of the different polymorphs of isotactic polypropylene, typically present in iPP crystallized under industrial processing conditions, is assessed. Different preparation strategies were used to obtain samples consisting of almost solely α, β, or γ crystals. X‐Ray measurements were used to validate that the desired phase was obtained. The intrinsic true stress ‐ true strain response of all individual phases was measured in uniaxial compression at several strain rates (deformation kinetics). Moreover, measurements were performed over a wide temperature range, covering the window in between the glass transition and the melting temperature. The relation between obtained yield stress and the strain rate is described with a modification of the Ree‐Eyring model. Differences and similarities in the deformation kinetics of the different phases are presented and discussed. Furthermore, the presence of three deformation processes, acting in parallel, is revealed. The Ree‐Eyring equation enables lifetime prediction for given thermal and mechanical conditions. These predictions were experimentally validated using constant load tests in uniaxial compression. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 729–747     

Synthesis,Chemical–Physical Characterization,and Biomedical Applications of Functional Gold Nanoparticles: A Review

Relevant properties of gold nanoparticles, such as stability and biocompatibility, together with their peculiar optical and electronic behavior, make them excellent candidates for medical and biological applications. This review describes the different approaches to the synthesis, surface modification, and characterization of gold nanoparticles (AuNPs) related to increasing their stability and available features useful for employment as drug delivery systems or in hyperthermia and photothermal therapy. The synthetic methods reported span from the well-known Turkevich synthesis, reduction with NaBH₄ with or without citrate, seeding growth, ascorbic acid-based, green synthesis, and Brust–Schiffrin methods. Furthermore, the nanosized functionalization of the AuNP surface brought about the formation of self-assembled monolayers through the employment of polymer coatings as capping agents covalently bonded to the nanoparticles. The most common chemical–physical characterization techniques to determine the size, shape and surface coverage of AuNPs are described underlining the structure–activity correlation in the frame of their applications in the biomedical and biotechnology sectors.     

Effect of SBS on Rheological Properties of Different Base Asphalts

In this note rheological properties of two different polymer modified asphalts (PMA) are compared. PMAs were prepared from two different base asphalts, a soft one (200/300 Pen grade) and a hard one (70/100 Pen grade), by addition of 4% by weight of radial SBS as modifier. Dynamic mechanical properties were determined in a wide temperature range for bases and modified asphalts both before and after artificial aging. As expected, the moduli of the soft base are more sensitive to polymer addition and the two PMAs attain similar maximum values after aging. However a significant difference in the frequency at which the maxima of the loss modulus are reached is maintained within the two materials irrespectively of aging or polymer addition.