This study demonstrates the possibility of forming 3D structures with enhanced thermal conductivity (k) by vat printing a silicone–acrylate based nanocomposite. Polydimethylsiloxane (PDSM) represent a common silicone-based polymer used in several applications from electronics to microfluidics. Unfortunately, the k value of the polymer is low, so a composite is required to be formed in order to increase its thermal conductivity. Several types of fillers are available to reach this result. In this study, boron nitride (BN) nanoparticles were used to increase the thermal conductivity of a PDMS-like photocurable matrix. A digital light processing (DLP) system was employed to form complex structures. The viscosity of the formulation was firstly investigated; photorheology and attenuate total reflection Fourier-transform infrared spectroscopy (ATR-FTIR) analyses were done to check the reactivity of the system that resulted as suitable for DLP printing. Mechanical and thermal analyses were performed on printed samples through dynamic mechanical thermal analysis (DMTA) and tensile tests, revealing a positive effect of the BN nanoparticles. Morphological characterization was performed by scanning electron microscopy (SEM). Finally, thermal analysis demonstrated that the thermal conductivity of the material was improved, maintaining the possibility of producing 3D printable formulations.
An extract of polyphenols was obtained from organic red grape pomace, chemically analyzed and used for functionalization of two bioactive glasses and porous hydroxyapatite. Functionalization is effective on hydroxyapatite and on the bioactive glass with higher surface reactivity with a different grafting mechanism.Grafting does not inhibit redox and radical scavenging activity of polyphenols. The grafted polyphenols make a continuous layer with an almost complete surface coverage. Polyphenols are released with different kinetics Accepted ArticleThis article is protected by copyright. All rights reserved according to the mechanism of grafting and maintain their redox activity. A homogeneous thin layer of polyphenols is still firmly grafted on both substrates after 28 days of soaking and it still maintains radical scavenging activity. The functionalized samples can be sterilized by gamma irradiation.
Chitosan is known for its specific antibacterial mechanism and biodegradability, while polyphenols are known for their antioxidant and anti-inflammatory properties: coupling these properties on a surface for bone contact, such as hydroxyapatite, is of great interest. The system developed here allows the combination of hydroxyapatite, chitosan, and polyphenol properties in the same multifunctional biomaterial in order to modulate the host response after implantation. Crosslinked chitosan is used in this research to create a stable coating on hydroxyapatite, and then it is functionalized for a smart release of the polyphenols. The release is higher in inflammatory conditions and lower in physiological conditions. The properties of the coated and functionalized samples are characterized on the as-prepared samples and after the samples are immersed (for 24 h) in solutions, which simulate the inflammatory and physiological conditions. Characterization is performed in order to confirm the presence of polyphenols grafted within the chitosan coating, the stability of grafting as a function of pH, the morphology of the coating and distribution of polyphenols on the surface, and the redox reactivity and radical scavenging activity of the functionalized coating. All the results are in line with previous results, which show a successful coating with chitosan and functionalization with polyphenols. Moreover, the polyphenols have a different release kinetics that is faster in a simulated inflammatory environment compared to that in the physiological environment. Even after the release tests, a fraction of polyphenols are still bound on the surface, maintaining the antioxidant and radical scavenging activity for a longer time. An electrostatic bond occurs between the negative-charged polar groups of polyphenols (carboxyls and/or phenols) and the positive amide groups of the chitosan coating, and the substitution of the crosslinker by the polyphenols occurs during the functionalization process.
The study aimed to identify an effective mechanism of adsorption of polyphenols on a nano-textured Ti surface and to evaluate the osteogenic differentiation on it. The source of polyphenols was a natural extract from red grape pomace. A chemical etching was used to form an oxide layer with a nanoscale texture on Ti; this layer is hydrophilic, but without hydroxyl groups with high acidic–basic chemical reactivity. The samples were characterized by electron and fluorescence microscopies, UV–Vis spectroscopy, contact angle measurements, zeta potential titration curves, and Folin–Ciocâlteu test. The presence of an adsorbed layer of polyphenols on the functionalized surface, maintaining redox ability, was confirmed by several tests. Consistent with the surface features, the adsorption was maximized by dissolving the extract in a high–amino acid medium, with respect to an inorganic solution, exploiting the high affinity of amino acids for polyphenols and for porous titanium surfaces. The osteogenic differentiation was assessed on an osteoblastic cell line by immunofluorescence, cell viability, expression of key osteoblast markers, and extracellular matrix mineralization. The surfaces functionalized with the extract diluted in the range 1 × 10−5–1 mg/mL resulted in having a greater osteogenic activity for the highest concentration, with lower values of cell viability; higher expression of alkaline phosphatase, bone sialoprotein, and collagen; and lower levels of osteopontin. In conclusion, the functionalization of a nano-textured Ti surface with polyphenols can potentially favor the osteogenic activity of osseointegrated implants.
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