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Partially covered self-expandable metallic esophageal stent (SEMS) placement is the most frequently applied palliative treatment in esophageal cancer. Structural characterization of explanted 16 nitinol-polyurethane SEMS (the group of 6 females, 10 males, age 40–80) was performed after their removal due to dysfunction. The adverse bulk changes in the polymer structure were identified using differential scanning calorimetry (DSC), differential mechanical thermal analysis (DMTA), and attenuated total reflectance infrared spectroscopy (ATR-IR) and discussed in terms of melting point shift (9 °C), glass-transition shift (4 °C), differences in viscoelastic behavior, and systematic decrease of peaks intensities corresponding to C–H, C═O, and C–N polyurethane structural bonds. The scanning electron and confocal microscopic observations revealed all major types of surface degradation, i.e., surface cracks, peeling off of the polymer material, and surface etching. The changes in the hydrophobic polyurethane surfaces were also revealed by a significant decrease in wettability (74°) and the corresponding increase of the surface free energy (31 mJ/m2). To understand the in vivodegradation, the in vitrotests in simulated salivary and gastric fluids were performed, which mimic the environments of proximal and distal ends, respectively. It was concluded that the differences in the degradation of the proximal and distal ends of prostheses strongly depend on the physiological environment, in particular stomach content. Finally, the necessity of the in vivotests for SEMS degradation is pointed out.

Proteins adsorbed onto biomaterial surfaces facilitate cell–material interactions, including adhesion and migration. Of particular importance are provisional matrix components, fibrinogen (Fg) and fibronectin (Fn), which play an important role in the wound-healing process. Here, to assess the potential of a series of elastomeric poly(butylene succinate) (PBS) copolymers for soft tissue engineering and regenerative medicine applications, we examined the adsorption of Fg and Fn. We prepared spin-coated thin films of the poly(butylene succinate) homopolymer and a series of elastomeric poly(butylene succinate) copolymers with butylene succinate (PBS, hard segment) to succinate-dimer linoleic diol unit (dilinoleic succinate (DLS), soft segments) weight ratios of 70:30, 60:40, and 50:50. X-ray diffraction was used to assess crystallinity, whereas the obtained thin films were characterized using a quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy. Protein adsorption was assessed using QCM-D, followed by data analysis using viscoelastic modeling. On all three copolymers, we observed robust adsorption of both key provisional matrix proteins. Importantly, for both proteins, viscoelastic modeling determined that the adlayers were 30–40 nm thick and had low shear modulus values (<25 kPa), thus indicating soft orientations (end-on for Fg) or conformations (open for Fn) of the hydrated proteins. Overall, our results are very encouraging, as they predict excellent cell adhesion and migration, key features enabling tissue integration of potential PBS-DLS scaffolds.

The present article investigates the use of a novel electrospun fibrous blend of poly(glycerol sebacate) (PGS) and poly(butylene succinate-butylene dilinoleate) (PBS-DLA) as a candidate for cardiac tissue engineering. Random electrospun fibers with various PGS/PBS-DLA compositions (70/30, 60/40, 50/50, and 0/100) were fabricated. To examine the suitability of these fiber blends for heart patches, their morphology, as well as their physical, chemical, and mechanical properties were measured before examining their biocompatibility through cell adhesion. The fabricated fibers were bead-free and exhibited a relatively narrow diameter distribution. The addition of PBS-DLA to PGS resulted in an increase of the average fiber diameter, whereas increasing the amount of PBS-DLA decreased the hydrophilicity and the water uptake of the nanofibrous scaffolds to values that approached those of neat PBS-DLA nanofibers. Moreover, the addition of PBS-DLA significantly increased the elastic modulus. Initial toxicity studies with C2C12 myoblast cells up to 72 h confirmed nontoxic behavior of the blends. Immunofluorescence analyses and scanning electron microscopy analyses confirmed that C2C12 cells showed better cell attachment and proliferation on electrospun mats with higher PBS-DLA content. However, immunofluorescence analyses of the 3-day-old rat cardiomyocytes cultured for 2 and 5 days demonstrated better attachment on the 70/30 fibers containing well-aligned sarcomeres and expressing high amounts of connexin 43 in cellular junctions indicating efficient cell-to-cell communication. It can be concluded, therefore, that fibrous PGS/PBS-DLA scaffolds exhibit promising characteristics as a biomaterial for cardiac patch applications.

The preparation of polymer nanocomposites filled with carbon nanotubes requires the nanotubes to be uniformly dispersed and compatible with the polymer matrix. In this work we report a preparation method of polyamide 6 (PA 6) based nanocomposite containing multi-walled carbon nanotubes (MWCNT) without any additional surface modification and obtained by in situ polymerization, as a simple method for composites production. The process was assisted by ultrasounds prior to synthesis.With such a method, an interesting morphology of polyamide 6 confined into a multiwalled carbon nanotube as well as grafted on a carbon nanotube surface was observed. For comparative purpose, PA 6 nanocomposites were also prepared from commercially available master batch by melt compounding.

New multiblock polymer-matrix nanocomposites were prepared by the in situ polycondensation. Polymers containing 30% hard segments of poly (butylene terephthalate) (PBT) and 70% soft segments built up from dimerized fatty acid (DLA), were modified with silica nanopowder. The nanocomposite materials were prepared by polycondensation in situ with the use of two different catalysts. Two types of nanosilica (Evonic Aerosil R 972 hydrophobic, and Aerosil 130 - hydrophilic) in amount of 0.1, 0.2 and 0.3 wt. % were used. Physical and mechanical properties were examined. The results indicate a strong influence of transesterification stoichiometry and type of catalyst on physical and mechanical properties. The amount of nanofiller and its character (hydrophilic or hydrophobic) showed also an influence on mechanical properties of synthesized nanocomposites indicating the best mechanical properties for nanocomposite containing 0.1wt% hydrophobic silica nanopowder (over 70% increase in elongation and 30% increase in tensile strength).

Influence of e-beam irradiation on the chemical and crystal structure of poly(aliphatic/aromatic-ester) multiblock thermoplastic elastomersPoly(aliphatic/aromatic-ester) (PED) multiblock copolymers belong to the class of thermoplastic elastomers (TPEs), characterized by a physical network of semi-crystalline hard segments. The PEDs were modified with e-beam to create an additional network structure. Polymers were evaluated using SEC, WAXS, DSC and quasi-static tensile tests. E-beam irradiation induced a significant increase of molecular weight and tensile strength of the PEDs. This effect, together with the diminished degree of crystallinity can be explained by the formation of chemical crosslinks, which are located in the hard phase segments.

Regeneration or repair of the damaged myocardium requires different strategies including engineered constructs for more efficient cell delivery. This study was undertaken to examine the potential of a new nanostructured elastomer to deliver embryonic stem cell‐derived cardiomyocytes (ESC‐CM) to an infarcted area of the myocardium. Engineered materials were biocompatible, mechanically stable, and elastomeric nanocomposites serving as substrates for delivery of ESC‐CM and as a left ventricular support device in myocardial regeneration strategies. Materials investigated were soft and strong poly(aliphatic/aromatic‐ester) multiblock thermoplastic elastomers with poly(ethylene terephthalate) (PET) hard segments and dimerized fatty acid, i.e., dilinoleic acid (DLA) soft segments, respectively, with and without addition of 0.2 wt% TiO2nanoparticles to form nanocomposites. The PET/DLA‐TiO2nanocomposite exhibited over 8 MPa tensile strength and 900% elongation at break. Addition of TiO2nanoparticles significantly altered surface roughness and enhanced adhesion and spreading of ESC‐CM derived from mouse and human embryonic stem cells. The newly developed materials did not affect the functional activity of spontaneously beating hESC‐CM, as demonstrated by unaltered rate of their beating, and the cells continued to demonstrate contractile activity on the materials for more than two months in culture (the longest time tested). Quantitative proliferation and survival assays using fibroblasts confirmed the ability of the new materials to support cells as well as or better than the present commercial‐type thermoplastic elastomer analog. The results indicate that PET/DLA and PET/DLA‐TiO2are promising candidates for the manufacture of engineered patches to deliver ESC‐CMs.

Fibroblasts proliferation and apoptosis as well as tissue response after implantation of elastomers containing nanocrystalline TiO2were investigated in the present in vitroand in vivostudy. Materials investigated were soft poly(aliphatic/aromatic‐ester) multiblock thermoplastic elastomers with poly(ethylene terephthalate) (PET) hard segments and dimerized linoleic acid (DLA) soft segments, respectively, containing 0.2 wt% TiO2nanoparticles. An investigation of the influence of TiO2nanoparticles incorporated into polymeric material on in vitrobiocompatibility revealed enhanced cell proliferation and diminished number of necrotic and apoptotic cells as compared to nanoparticles‐free polymer. Implantation tests indicated that the observed tissue changes were similar to those observed with medical‐grade silicone elastomer, no evidence of contact necrosis being observed. The unchanged morphology of rat liver hepatocytes and the lack of parenchymal necrosis also indicated that exposure to the material containing TiO2nanoparticles, did not cause any cytotoxic reactions. The present study, thus, showed that elastomeric polyester containing TiO2nanoparticles are interesting biomimetic constructs for improved tissue regeneration.

This paper will discuss the biocompatibility and dynamic fatigue properties of polystyrene-b-polyisobutylene-b-polystyrene thermoplastic elastomer with 30 wt % polystyrene (SIBS30), an emerging FDA-approved biomaterial. SIBS30 is a very soft, transparent biomaterial resembling silicone rubber, with superior mechanical properties. Using the hysteresis method adopted for soft biomaterials, the dynamic fatigue properties of SIBS30 were found to be between those of polyurethane and silicone rubber, with fatigue life twice as long as that of silicone. Under single load testing (SLT, 1.25 MPa), SIBS30 displayed less than half the dynamic creep compared to silicone, both in air and in vitro (37 °C, simulated body fluid). Hemolysis and 30- and 180-day implantation studies revealed excellent biocompatibility of the new biomaterial. The results presented in this paper indicate that, in comparison with silicone rubber, SIBS30 has similar biocompatibility and superior dynamic fatigue properties.

Synthesis and thermal properties of poly(aliphatic/aromatic‐ester) copolymers containing additionally poly(dimethylsiloxane) (PDMS) chains in the soft segments are discussed. A two step method of transesterification and polycondensation from the melt was carried out in a presence of magnesium‐titanate catalyst. An aliphatic dimer fatty acid was used as a component of the soft segments while poly(butylene terephthalate) (PBT) constituted the hard blocks. Effectiveness of the incorporation of PDMS into polymer chain was confirmed by the Soxhlet extraction and infrared spectroscopy of an excess of 1,4‐butane diol destilled off from the polycondensation reaction. Multiblock copolymers showed microphase separation as determined by differential scanning calorimetry. Incorporation of a small amount of PDMS (up to 14.5 wt.‐%) into polymer chain containg low concentration of hard segments of PBT lead to decrease in crystallinity of such copolymers. This may indicate that semicrystalline PBT are dissolved in the amorphous matrix of the soft segments.

The melt polycondensation method was investigated for the synthesis of a multiblock copolymer. The copolymer consisted of hard segments of poly(butylene terephthalate) (PBT) and soft segments of dimerised fatty acid. This multiblock copolymer was characterised by 1H and 13C NMR and FTIR spectroscopies and differential scanning calorimetry. The 1H NMR method was used for estimating quantitatively the amount of the hard/soft segments. The polymer morphology was characterised using light microscopy and transmission electron microscopy. The investigated polymer was used in a small amount as an additive to poly(propylene)/PBT blends in order to evaluate its influence on the morphology and impact properties of these blends.