Polycaprolactone/gelatin-based scaffolds with tailored performance: in vitro and in vivo validation.

Nanofibrous scaffolds composed of polycaprolactone (PCL) and gelatin (Ge) were obtained through a hydrolytic assisted electrospinning process. The PCL-to-Ge proportion (100/0 to 20/80), as well as the dissolution time (24, 48, 72, 96, 120 h) into a 1:1 formic/acetic acid solvent before electrospinning were modified to obtain the different samples. A strong influence of these factors on the physicochemical properties of the scaffolds was observed. Higher Ge percentage reduced crystallinity, allowed a uniform morphology and increased water contact angle. The increase in the dissolution time considerably reduced the molar mass and, subsequently, fibre diameter and crystallinity were affected. During in vitro biocompatibility tests, higher cell adhesion and proliferation were found for the 60/40, 50/50 and 40/60 PCL/Ge compositions that was corroborated by MTT assay, fluorescence and microscopy. A weakened structure, more labile to the in vitro degradation in physiologic conditions was found for these compositions with higher dissolution times (72 and 96 h). Particularly, the 40/60 PCL/Ge scaffolds revealed an interesting progressive degradation behaviour as a function of the dissolution time. Moreover, these scaffolds were non-inflammatory, as revealed by the pyrogen test and after the 15-day subcutaneous in vivo implantation in mice. Finally, a reduction of the scar tissue area after infarction was found for the 40/60 PCL/Ge scaffolds electrospun after 72 h implanted in rat hearts. These results are especially interesting and represent a feasible way to avoid undesired inflammatory reactions during the scaffold assimilation.

Reprocessed polylactide: studies of thermo-oxidative decomposition.

The combustion process of virgin and reprocessed polylactide (PLA) was simulated by multi-rate linear non-isothermal thermogravimetric experiments under O(2). A complete methodology that accounted on the thermal stability and emission of gases was thoroughly developed. A new model, Thermal Decomposition Behavior, and novel parameters, the Zero-Decomposition Temperatures, were used to test the thermal stability of the materials under any linear heating rate. The release of gases was monitored by Evolved Gas Analysis with in-line FT-IR analysis. In addition, a kinetic analysis methodology that accounted for variable activation parameters showed that the decomposition process could be driven by the formation of bubbles in the melt. It was found that the combustion technologies for virgin PLA could be transferred for the energetic valorization of its recyclates. Combustion was pointed out as appropriate for the energetic valorization of PLA submitted to more than three successive reprocessing cycles.

A methodology to assess the energetic valorization of bio-based polymers from the packaging industry: pyrolysis of reprocessed polylactide.

The energetic valorization process of bio-based polymers is addressed in this study, taking polylactide (PLA) as model. The pyrolysis of virgin and multiple-injected PLA was simulated by means of multi-rate linear-non-isothermal thermogravimetric experiments. A complete methodology, involving control of gases, thermal stability and thermal decomposition kinetics was proposed. The release of gases was monitored by Evolved Gas Analysis of the fumes of pyrolysis, by in-line FT-IR, with the aid of 2D-correlation IR characterization. A novel model to establish the thermal stability of PLAs under any linear heating profile was proposed. A kinetic strategy was methodically applied to assess the thermal decomposition in terms of activation energy and kinetic model. It was found that the pyrolysis technologies for virgin PLA could be straightforwardly transferred for the valorization of its recyclates.

A statistical design of experiments for optimizing the MALDI-TOF-MS sample preparation of polymers. An application in the assessment of the thermo-mechanical degradation mechanisms of poly (ethylene terephthalate).

The sample preparation procedure for MALDI-TOF MS of polymers is addressed in this study by the application of a statistical Design of Experiments (DoE). Industrial poly (ethylene terephthalate) (PET) was chosen as model polymer. Different experimental settings (levels) for matrixes, analyte/matrix proportions and concentrations of cationization agent were considered. The quality parameters used for the analysis were signal-to-noise ratio and resolution. A closer inspection of the statistical results provided the study not only with the best combination of factors for the MALDI sample preparation, but also with a better understanding of the influence of the different factors, individually or in combination, to the signal. The application of DoE for the improvement of the MALDI measure of PET stated that the best combination of factors and levels was the following: matrix (dithranol), proportion analyte/matrix/cationization agent (1/15/1, V/V/V), and concentration of cationization agent (2 g L(-1)). In a second part, multiple processing by means of successive injection cycles was used to simulate the thermo-mechanical degradation effects on the oligomeric distribution of PET under mechanical recycling. The application of MALDI-TOF-MS showed that thermo-mechanical degradation primarily affected initially predominant cyclic species. Several degradation mechanisms were proposed, remarking intramolecular transesterification and hydrolysis. The ether links of the glycol unit in PET were shown to act as potential reaction sites, driving the main reactions of degradation.