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This research work proposes a synergistic approach to improve implants' performance through the use of porous Ti substrates to reduce the mismatch between Young's modulus of Ti (around 110 GPa) and the cortical bone (20-25 GPa), and the application of a biodegradable, acrylic acid-based polymeric coating to reduce bacterial adhesion and proliferation, and to enhance osseointegration. First, porous commercially pure Ti substrates with different porosities and pore size distributions were fabricated by using space-holder techniques to obtain substrates with improved tribomechanical behavior. On the other hand, a new diacrylate cross-linker containing a reduction-sensitive disulfide bond was synthesized to prepare biodegradable poly(acrylic acid)-based hydrogels with 1, 2, and 4% cross-linker. Finally, after the required characterization, both strategies were implemented, and the combination of 4% cross-linked poly(acrylic acid)-based hydrogel infiltrated in 30 vol % porosity, 100-200 μm average pore size, was revealed as an outstanding choice for enhancing implant performance.

In this research work, the fabrication of biphasic composite implants has been investigated. Porous, commercially available pure Ti (50 vol % porosity and pore distributions of 100-200, 250-355, and 355-500 μm) has been used as a cortical bone replacement, while different composites based on a polymer blend (gelatin and alginate) and bioactive glass (BG) 45S5 have been applied as a soft layer for cartilage tissues. The microstructure, degradation rates, biofunctionality, and wear behavior of the different composites were analyzed to find the best possible coating. Experiments demonstrated the best micromechanical balance for the substrate containing 200-355 μm size range distribution. In addition, although the coating prepared from alginate presented a lower mass loss, the composite containing 50% alginate and 50% gelatin showed a higher elastic recovery, which entails that this type of coating could replicate the functions of the soft tissue in areas of the joints. Therefore, results revealed that the combinations of porous commercially pure Ti and composites prepared from alginate/gelatin/45S5 BG are candidates for the fabrication of biphasic implants not only for the treatment of osteochondral defects but also potentially for any other diseases affecting simultaneously hard and soft tissues.

The porous substrates of commercially pure titanium have been coated with a novel bilayer of bioactive glasses (BGs), 45S5 and 1393, to improve the osseointegration and solve the stress-shielding phenomenon of titanium partial implants. The porosity of the substrates and the scratch resistance and bioactivity of the coating have been evaluated. Results are discussed in terms of stiffness and yield strength of the substrates, as well as the chemical composition, thickness, and design of the bioglass coating (monolithic vs bilayer). The role of the pores was a crucial issue in the anchoring of the coating, both in porosity percentage (30 and 60 vol %) and in pore range size (100-200 and 355-500 μm). The study was focused on the adhesion and infiltration of a 1393 bioglass layer (in contact with a porous titanium substrate), in combination with the biofunctionality of the 45S5 bioglass layer (surrounded by the host bone tissue), as 1393 bioglass enhances the adherence, while 45S5 bioglass promotes higher bioactivity. This bioactivity of the raw powder was initially estimated by nuclear magnetic resonance, through the evaluation of the chemical environments, and confirmed by the formation of hydroxyapatite when immersed in a simulated body fluid. The results revealed that the substrate with 30 vol % of porosity and a range of 355-500 μm pore size, coated with this novel BG bilayer, presented the best combination in terms of mechanical and biofunctional properties.

The synthesis, characterization, and some properties of new glutathione-mediated biodegradable sugar-based copolyurethanes are described. These copolyurethanes were obtained by polyaddition reaction of mixtures of 2,2'-dithiodiethanol (DiT) and 2,3,4-tri-O-benzyl-L-arabinitol (ArBn) or 2,3,4-tri-O-methyl-L-arabinitol (ArMe) to 1,6-hexamethylene diisocyanate (HMDI). The copolymer compositions were studied by elemental microanalyses and (1)H NMR, revealing that the content of the copolymer units is in all cases very similar to that of their corresponding feed. The PU(DiT-HMDI) homopolymer exhibited a high crystallinity, but the introduction of the arabinitol-based diols led to a reduction in the crystallinity of the copolymers. In their TG curves, the copolymers exhibited a mixed trend of the related homopolymers, and all of them were thermally stable, with degradation temperatures above 220 degrees C. The degradation properties of the macromolecules under physiological conditions in the presence of glutathione were tested. All the copolyurethanes proved to be biodegradable under the experimental conditions (pH = 7.02 and 37 degrees C). The degradation pattern of the copolymers depended not only on the dithiodiethanol (DiT) reactive units ratio in the polymer backbone, but also on the crystallinity of the macromolecule.