Scaffolds are three-dimensional porous structures that must have specific requirements to be applied in tissue engineering. Therefore, the study of factors affecting scaffold performance is of great importance. In this work, the optimal conditions for cross-linking preformed chitosan (CS) scaffolds by the tripolyphosphate polyanion (TPP) were investigated. The effect on scaffold physico-chemical properties of different concentrations of chitosan (1 and 2% w/v) and tripolyphosphate (1 and 2% w/v) as well as of cross-linking reaction times (2, 4, or 8 h) were studied. It was evidenced that a low CS concentration favored the formation of three-dimensional porous structures with a good pore interconnection while the use of more severe conditions in the cross-linking reaction (high TPP concentration and crosslinking reaction time) led to scaffolds with a suitable pore homogeneity, thermal stability, swelling behavior, and mechanical properties, but having a low pore interconnectivity. Preliminary biocompatibility tests showed a good osteoblasts’ viability when cultured on the scaffold obtained by CS 1%, TPP 1%, and an 8-h crosslinking time. These findings suggest how modulation of scaffold cross-linking conditions may permit to obtain chitosan scaffold with properly tuned morphological, mechanical and biological properties for application in the tissue regeneration field.
An innovative consolidation strategy for degraded paper is presented based on the reversible application of cellulose nanocrystals as sustainable fillers to reinforce mechanical properties and resistance to further degradation. The compatibility and efficacy of the proposed consolidation treatment are assessed first on pure cellulose paper, used as a model, by reliable techniques such as field emission scanning electron microscopy, atomic force microscopy, tensile tests, X-ray powder diffraction, and Fourier transform infrared spectroscopy, evidencing the influence of the surface functionalization of nanocellulose on the consolidation and protection effects. Then, the consolidation technique is applied to real aged paper samples from Breviarium romanum ad usum Fratrum Minorum S.P. ( 1738), demonstrating the promising potential of the suggested approach. Amperometric measurements, carried out with a smart electrochemical tool developed in our laboratory, demonstrate the reversibility of the proposed treatment by removal of the nanocrystalline cellulose from the paper surface with a suitable cleaning hydrogel. This completely new feature of the consolidation treatment proposed here satisfies a pivotal requisite in cultural heritage conservation because the methodological requirement for the ″reversibility″ of any conservation measure is a fundamental goal for restorers. A paper artifact, in fact, is subject to a number of natural and man-made hazards, inducing continuous degradation. With time, monitoring and consolidation actions need to be often performed to ensure conservation, and this tends to modify the status quo and compromise the artifact integrity. Removable treatments can potentially avoid erosion of the artifact integrity.
The utilization of food waste and sewage sludge as organic substrate from urban context for the synthesis of microbial polyhydroxyalkanoates (PHAs) has been only recently investigated at pilot scale. Within this context, two stabilization methods have been found for preserving the amount of PHA intracellularly produced by open mixed microbial culture (MMC): thermal drying and wet acidification of the biomass at the end of PHA accumulation process. The extracted PHA from the two differently stabilized biomasses was then characterized with regard to chemical composition, molecular weight, and thermal properties. The polymer contained two types of monomers, namely 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3HV) at a relative percentage of 93.0–79.8 and 7.0–20.2 w/w, respectively. PHA extracted from wet-acidified biomass had higher average molecular weights (Mw) of 370–424 kDa while PHA recovered from thermally stabilized dried biomass had a 3-fold lower Mw (on average). The PHA decomposition temperatures Td10% and Tdmax were in the range 260–268 °C and 269–303 °C, respectively, not dependent on the monomeric composition or molecular weight. Thermal properties such as melting temperature (Tm1 132–150 °C; Tm2 155–167 °C) and melting enthalpy (26–70 J/g) were quantified in a relatively broad range according to the different stabilization-extraction method and obtained composition.
We report on the thermodynamic, structural and dynamic properties of a recently proposed Deep Eutectic Solvent (DES), formed by choline acetate and urea at the stoichiometric ratio 1:2, hereinafter indicated as acetaline. Acetaline, although melting at ca. 40 °C, can be easily supercooled in its liquid state at sub-ambient conditions. The existence of a crystalline phase has been detected, together with the glass-liquid transition at -50 °C. Synchrotron high energy X-ray scattering experiments provide the experimental data for supporting a Reverse Monte Carlo analysis to extract structural information at atomistic level. This exploration of acetaline's liquid structure reveals the major role played by hydrogen bonding in determining interspecies correlations: both acetate and urea are strong hydrogen bond acceptor sites, while both the choline hydroxyl and urea act as HB donors. All acetaline moieties are involved in mutual interactions, with acetate and urea strongly interacting through hydrogen bonding, while choline being involved mostly in van der Waals mediated interactions. Such a structural situation is mirrored by the dynamic evidences obtained by means of 1 H NMR techniques, that show how urea and acetate species experience higher translational activation energy than choline, fingerprinting their stronger commitments into the extended hydrogen bonding network established in acetaline.
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