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In the quest for advancing the performance of metallic implants, surface modification emerges as a pivotal strategy to mitigate ion depletion, enhance the host's biological response, and exhibit anti-microbial behavior with reduced cytotoxicity. In this study, we developed a non-traditional electrophoretic deposition (EPD) hybrid coating for medical-grade stainless steel 316 L (SS316L) surfaces covered with a segmented polyurethane (SPU). These coatings are composed of anatase TiO₂ nanotubes (TiO₂_A), and antibiotics (nisin N or gentamicin G). We characterized the modified metals using FTIR and Raman spectroscopy, contact angle measurements, AFM, TGA, SEM-EDX, as well as assessing their antimicrobial response and cell cytotoxicity. The results demonstrate the formation of porous surfaces with embedded nanotubes and antibiotics within and on the polyurethane surfaces. Samples with SPU+ TiO₂_AG EPD exhibited superior coverage, antimicrobial properties, and enhanced viability compared to cases where only particles or antibiotics were coated individually. Additionally, samples of SPU+ TiO₂_AN EPD displayed favorable hydrophilicity and suitable cytotoxicity. Therefore, the synergistic effect of nanoparticles and antibiotics positively influences the functionality of the coating.

The electrical, mechanical and piezoresistive responses of vinyl ester nanocomposites made of two types of multilayer graphene sheets (GSs) and multiwall carbon nanotube hybrid fillers at different relative concentrations is presented. Two types of GSs are used in order to evaluate the role of their physicochemical properties. The best mechanical properties were achieved with hybrids at 75% relative concentration of GSs. Collaborative effects were also observed in the electrical conductivity of the hybrids at this relative concentration. The flexural piezoresistive response yielded low sensitivity (with both, positive and negative gage factors) at the compression side of the flexural coupon. On the contrary, the tensile side of the coupon always presented positive resistance changes and significantly higher piezoresistive sensitivity. The highest piezoresistive sensitivity was found for hybrid materials with 75% relative concentration of GSs, using the graphenic sheets with larger lateral dimensions and higher structural quality (lower Raman I/I ratio).

Two main problems limit the success of titanium implants: bacterial infection, which restricts their osseointegration capacity; and the stiffness mismatch between the implant and the host cortical bone, which promotes bone resorption and risk of fracture. Porosity incorporation may reduce this difference in stiffness but compromise biomechanical behavior. In this work, the relationship between the microstructure (content, size, and shape of pores) and the antibacterial and cellular behavior of samples fabricated by the space-holder technique (50 vol % NH4HCO3 and three ranges of particle sizes) is established. Results are discussed in terms of the best biomechanical properties and biofunctional activity balance (cell biocompatibility and antibacterial behavior). All substrates achieved suitable cell biocompatibility of premioblast and osteoblast in adhesion and proliferation processes. It is worth to highlighting that samples fabricated with the 100–200 μm space-holder present better mechanical behavior—in terms of stiffness, microhardness, and yield strength—which make them a very suitable material to replace cortical bone tissues. Those results exposed the relationship between the surface properties and the race of bacteria and mammalian cells for the surface with the aim to promote cellular growth over bacteria.

Segmented polyurethanes based on polycaprolactone, 4,4 (metylene-bis-cyclohexyl) isocyanate, and L-lysine were synthesized, manufactured as small vascular grafts and characterized according to ISO 7198 standard for cardiovascular implants—tubular vascular prosthesis. In terms of mechanical properties, the newly synthesized polyurethane films exhibited lower secant modulus than Tecoflex™ SG 80A, a well-known medical grade polyurethane. Similarly, when tested as grafts, the L-lysine-based polyurethane exhibited lower longitudinal failure load (11.5 N vs. 116 N), lower circumferential failure load per unit length (5.67 N/mm vs. 14.0 N/mm) and lower suture forces for both nylon (13.3 N vs. 24.0 N) and silk (14.0 N vs. 19.3 N) when compared to Tecoflex™ SG 80A grafts. L-Lysine-based graft exhibited a burst strength of 3620 mmHg (482.6 kPa) and a compliance of 0.16%/mmHg. The cell adhesion was demonstrated with NIH/3T3 fibroblasts where cell adhesion was observed on both films and grafts, while cell alignment was observed only on the grafts. The mechanical properties of this polyurethane and the possibility of strain-induced PCL crystals as the switching phase for shape memory materials, allowed a strain recovery ratio and a strain fixity ratio with values higher than 95% and 90%, respectively, with a repeatability of the shape-memory properties up to 4 thermo-mechanical cycles. Overall, the properties of lysine-based polyurethanes are suitable for large diameter vascular grafts where cell alignment can be controlled by their shape memory potential.

[EN] Electrospun polycaprolactone (PCL)/chitosan (CH) blend scaffolds with different CH weight ratios were prepared to study the effect of scaffold composition on its physicochemical and biological properties. Scanning electron microscopy showed bead-free homogeneous randomly arranged nanofibers whose average diameter decreased from 240 to 110 nm with increasing CH content. The infrared spectra of the PCL/CH blends were very similar to the neat PCL scaffold. Energy-dispersive x-ray spectroscopy analysis confirmed the presence of carbon, oxygen and nitrogen in the scaffolds, although fluorine-from chemicals used as solvent-was also detected. The water contact angle decreased from 113 degrees (for PCL) to 52 degrees with increasing chitosan content. The biocompatibility was evaluated using fibroblasts and Schwann cell (SC) cultures. Cytotoxicity assays using fibroblasts demonstrated that electrospun scaffolds could be considered as non-cytotoxic material. Biocompatibility tests also revealed that the SCs adhered to scaffolds with different CH content, although the formulation containing CH at 5 wt% exhibited the highest proliferation on days 1 and 3. A better cell distribution was observed in the CH/PCL blends than in the neat PCL or CH scaffolds, where the cells were clustered. Immunochemistry analysis confirmed that SCs expressed the specific p75 cell marker on the scaffolds, suggesting that PCL/CH scaffolds would be good candidates for peripheral nerve tissue engineering.

The synthesis of novel polyurethanes is a subject of increasing interest, especially those that involve biologically active molecules. Generally, the reports on the synthesis of segmented polyurethanes using modified amino acids as chain extenders assume that the reaction occurs due to functionalities (OH and NH2) of the last compounds. However, few works really prove the reaction takes place with unmodified amino acids. In this work, spectroscopic techniques such as 1H, 13C, and 1H-1H COSY NMR and FTIR were used to chemical characterization of poly(ureaamide)urethanes synthesized from polycaprolactone diol (PCL diol 530), 4,4¿-methylene-bis(cyclohexyl isocyanate) (H12MDI), and amino acids such as L-arginine, glycine or L-aspartic acid as chain extenders. In addition, model compounds (without PCL diol) were analyzed to confirm reaction of amino acids via urea and amide formation. Additionally, the polymers exhibited different physicochemical and mechanical properties depending on the chain extender used. These results suggest that unmodified amino acids can be used as chain extenders in the synthesis of poly(amide-urea) urethanes for biomedical applications

Dimecres serem a Palamós per acompanyar en alta mar uns investigadors de l'Institut de Ciències del Mar que estudien com minimitzar l'impacte de les barques de pesca sobre les gambes. Arran d'un informe del geòleg blanenc Pere Puig, els pescadors han pres consciència de com es fa malbé el fons marí i ara estan mirant de redreçar la situació. Rafel Bagot ha pujat al vaixell per veure "in situ" què hi fan aquests científics, i ens ho explicarà en detall en el programa

This paper describes the preparation and characterization of water-soluble urethane oligomers bearing protected isocyanate groups. It also points out its ability to crosslink decellularized pericardium, as a model collagen scaffold, and to adjust their structural characteristics. A library of oligourethanes was synthesized by varying the molecular weight (Mw 400, 600, 1000 or 2000 g mol-1) of the poly(ethylene glycol) and the type of aliphatic diisocyanate (isophorone diisocyanate/IPDI or hexamethylene diisocyanate/HDI). 1H and 13C NMR, FTIR and mass spectrometry demonstrated that the crosslinkers are composed of chains with carbamoylsulfonate end groups that have trimeric and pentameric oligourethanes, and monomeric diisocyanate. The degree of crosslinking and hence the in vitro degradation susceptibility of the decellularized pericardium were inversely related to the Mw of the oligourethanes. The toxicity of the extractable products from oligourethane-collagen materials toward fibroblasts and macrophages was found to be lower for the crosslinker derived from IPDI than for those derived from HDI. On the other hand, the resistance to collagenase or oxidative degradation of the bovine pericardium crosslinked with HDI/oligourethane was higher than the one prepared with IPDI/oligourethane. As the Mw of the oligomers regulates the degree of crosslinking while the chemical composition influences the cytocompatibility and biodegradation of decellularized pericardium, these urethane oligomers can be used as safer crosslinkers for other protein-based biomaterials. © 2014 the Partner Organisations.

The present study investigates the potential use of non-catalyzed water-soluble blocked polyurethane prepolymer (PUP) as a bifunctional cross-linker for collagenous scaffolds. The effect of concentration (5, 10, 15 and 20%), time (4, 6, 12 and 24 h), medium volume (50, 100, 200 and 300%) and pH (7.4, 8.2, 9 and 10) over stability, microstructure and tensile mechanical behavior of acellular pericardial matrix was studied. The cross-linking index increased up to 81% while the denaturation temperature increased up to 12 °C after PUP crosslinking. PUP-treated scaffold resisted the collagenase degradation (0.167 ± 0.14 mmol/g of liberated amine groups vs. 598 ± 60 mmol/g for non-cross-linked matrix). The collagen fiber network was coated with PUP while viscoelastic properties were altered after cross-linking. The treatment of the pericardial scaffold with PUP allows (i) different densities of cross-linking depending of the process parameters and (ii) tensile properties similar to glutaraldehyde method.

Bovine pericardium is a collagenous tissue commonly used as a natural biomaterial in the fabrication of cardiovascular devices. For tissue engineering purposes, this xenogeneic biomaterial must be decellularized to remove cellular antigens. With this in mind, three decellularization protocols were compared in terms of their effectiveness to extract cellular materials, their effect on glycosaminoglycan (GAG) content and, finally, their effect on tensile biomechanical behavior. The tissue decellularization was achieved by treatment with t-octyl phenoxy polyethoxy ethanol (Triton X-100), tridecyl polyethoxy ethanol (ATE) and alkaline treatment and subsequent treatment with nucleases (DNase/RNase). The quantified residual DNA content (3.0 ± 0.4%, 4.4 ± 0.6% and 5.6 ± 0.7% for Triton X-100, ATE and alkaline treatment, respectively) and the absence of nuclear structures (hematoxylin and eosin staining) were indicators of effective cell removal. In the same way, it was found that the native tissue GAG content decreased to 61.6 ± 0.6%, 62.7 ± 1.1% and 88.6 ± 0.2% for Triton X-100, ATE and alkaline treatment, respectively. In addition, an alteration in the tissue stress relaxation characteristics was observed after alkaline treatment. We can conclude that the three decellularization agents preserved the collagen structural network, anisotropy and the tensile modulus, tensile strength and maximum strain at failure of native tissue.

In this work, the combined influence of barium sulfate content and co-monomer concentration on the properties of acrylic bone cement for percutaneous vertebroplasty (PVP) was investigated using a response surface methodology. Cements were prepared with methyl methacrylate (MMA) and either diethyl amino ethyl methacrylate (DEAEM) or dimethyl amino ethyl methacrylate (DMAEM) as co-monomer in the liquid phase, while variable amounts of barium sulfate were incorporated to the solid phase in order to improve the radiopacity of cements. It was found that various properties such as peak temperature, setting time, residual monomer content, mechanical properties and injectability, had an effect on the occurrence of interactions (combined effect) between the barium sulfate and DEAEM in bone cements formulations when independent variables were at their maximum. © Koninklijke Brill NV, Leiden, 2011.

Nanocomposites prepared with segmented polyurethane (SPU) and commercially available nanoclays (Cloisite™ Na+, Cloisite™ 15A, Cloisite™ 30B) were studied using thermogravimetric analysis coupled with Fourier Transform Infrared Spectroscopy (TGA/FTIR). The results showed that the thermal degradation of unfilled SPU and the 4, 6 and 10 wt% hand mixed nanocomposites occurred in two stages being the first due to degradation of hard segments and the second due to the degradation of soft segments. It was also found that the thermal stability of these nanocomposites was not improved by increasing nanoclay concentration except for SPU/Cloisite™ 15A nanocomposites were a 40 °C increase was observed. In a similar manner, FTIR spectra of the evolved gases obtained after the thermal degradation of these nanocomposites were qualitatively similar to the unfilled polymer except in those containing Cloisite™ 30B where isocyanate absorptions were detected. In contrast, SPU/Cloisite™ 30B nanocomposites prepared by in-situ polymerization, exhibited higher thermal stability than the corresponding hand mixed nanocomposites. In addition, these nanocomposites exhibited the presence of carbon dioxide in the evolved gases during its second degradation stage which was not observed in the hand mixed nanocomposites. In this case, it can be said that the presence of clays in the nanocomposites has a significant effect on the thermal degradation pathways.

The thermal degradation behavior of polymethacrylates containing amine groups such as poly(N,N-diethyl aminoethyl methacrylate), PDEAEM, and poly(N-ethyl-m-tolyl-aminoethyl methacrylate), PMEET, has been studied using thermogravimetry coupled with infrared spectroscopy (TGA/FTIR). PDEAEM showed two degradation stages whereas PMEET displayed only one. The thermal degradation of PDEAEM initially takes place through ester cleavage of the polymethacrylate, generating volatile tertiary amines and alcohols and polymethacrylic anhydride in the remaining solid material. This is followed by further fragmentation of the modified polymeric chain formed. It was also observed that storage of the original polymer affected the thermal decomposition behavior of PDEAEM. The main thermal degradation pathway for PMEET is an immediate backbone chain scission to yield oligomers.