Pyrene-end-functionalized poly(L-lactide) as an efficient carbon nanotube dispersing agent in poly(L-lactide): mechanical performance and biocompatibility study.

In order to improve the mechanical properties of poly(L-lactide) (PLLA) based implants, a study was made of how far well dispersed multi-walled carbon nanotubes (MWCNTs) within a PLLA matrix were able to positively affect these properties. To this end, pyrene-end-functionalized poly(L-lactide) (py-end-PLLA) was evaluated as a dispersing agent. Transmission electron microscopy (TEM) analyses and mechanical tests of MWCNTs-based materials demonstrated an enhancement of MWCNT dispersion in the PLLA matrix and improved Young's modulus (E) when 4 wt% of py-end-PLLA was used as the dispersing agent. Subsequently, the bioacceptance of PLLA/py-end-PLLA/MWCNTs nanocomposites was evaluated using human bone marrow stromal cells (HBMC) in vitro. The inclusion of py-end-PLLA and MWCNTs supported HBMC adhesion and proliferation. The expression levels of the bone-specific markers indicated that the cells kept their potential to undergo osteogenic differentiation. The results of this study indicate that the addition of MWCNT combined with py-end-PLLA in PLLA/py-end-PLLA/MWCNTs nanocomposites may widen the range of applications of PLLA within the field of bone tissue engineering thanks to their mechanical strength and cytocompatibility.

Study of the chain microstructure effects on the resulting thermal properties of poly(L-lactide)/poly(N-isopropylacrylamide) biomedical materials.

The development of thermally-sensitive poly(N-isopropylacrylamide) (PNIPAAm) and biocompatible/biodegradable poly(L-lactide) (PLLA) blends offers us an efficient strategy in order to obtain materials with improved functional properties to be used in the emerging field of biomedicine. In this sense, thermal properties of PLLA and PNIPAAm have been investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and wide angle X-ray diffraction (WAXD) were conducted to shed more light on the obtained results. For a better understanding of PLLA/PNIPAAm system, both low and high molecular weight PLLA and PNIPAAm have been synthesized by ring opening polymerization and aqueous redox polymerization respectively. Obtained results are interpreted from the viewpoint of chain microstructure of each homopolymer and the ratio between two constituent materials. DSC, SEM and WAXD results show a phase separation over the entire composition range irrespectively of the molecular weight of both homopolymers. Additionally, it was found a nucleating agent behavior of low molecular weight PNIPAAm, while high molecular weight PNIPAAm hinders the crystallization of PLLA. FTIR results suggest that the strong autoassociation present in PNIPAAm plays a key role impairing the miscibility of the whole system. Thermogravimetric analysis reveals that thermodegradation process of PLLA could be continuously delayed with the addition of PNIPAAm due to the increased thermal stability of N-isopropylacrylamide in regard to L-lactide sequences.

Improvement of toughness by stereocomplex crystal formation in optically pure polylactides of high molecular weight.

A solution casting method followed by thermal homogenization was performed for the preparation of 1:1 blends and non-blended films from poly(d-lactide) (PDLA) and poly(l-lactide) (PLLA) of three different molecular weights, and their thermal and mechanical properties were determined via differential scanning calorimetry (DSC) and tensile tests. According to the literature, when Mw is below 1.0×10(5)g/mol only stereocomplex crystallization takes place, and when it is higher, both homocrystallites and stereocomplex crystallites co-exist. In order to promote crystallization as a homocrystal in neat polylactides and to promote the stereoselective crystallization as stereocomplex in the case of non-blended films, and in turn, to achieve different degrees of crystallinity, several thermal treatments of annealing were carried out in this work. Highly stereocomplexed blends were found by the stereospecific thermal treatments. As a consequence, the toughness of 1:1 blends was found significantly enhanced over those of non-blended films, irrespective of molecular weight. For instance, in B2-5050 stereocomplexed blend having poly(l-lactide) and poly(d-lactide) of Mw=1.2×10(5)g/mol, tensile strength increased from 44.0±2.1MPa to 65.1±6.1MPa, and the elongation at break from 10.8±2.5% to 33.1±8.1% with respect to its non-blended poly(l-lactide) counterpart crystallized as homocrystal. This improvement in mechanical properties in stereocomplexed blends is not attributed to the inherent properties of the type of crystal polymorph but to the presence of a higher density of intercrystalline connections through a mobile amorphous phase, i.e. tie chains in the stereocomplexed supramolecular spherulitic entities that provide in the stereocomplexed samples enhanced strength and elongation at break at the same time.

Conformational behavior of poly(L-lactide) studied by infrared spectroscopy.

This paper reports the analysis of the C=O stretching region of poly(L-lactide). This spectral band splits into up to four components, a phenomenon that a priori can be explained in terms of carbonyl-carbonyl coupling or specific interactions (such as C-H...O hydrogen bonding or dipole-dipole). Hydrogen bonding can be discarded from the analysis of the C-H stretching spectral region. In addition, low molecular weight dicarbonyl compounds of chemical structure similar to that of PLLA, such as diacyl peroxides, show a remarkable splitting of the carbonyl band attributed to intramolecular carbonyl-carbonyl coupling. Several mechanisms can be responsible for this behavior, such as mechanical coupling, electronic effects, or through-space intramolecular TDC (transition dipole coupling) interactions. Intermolecular dipole-dipole interactions (possible in the form of interchain TDC interactions) are proven to be of minor relevance taking into account the spatial structure of the PLLA conformers. The Simply Coupled Oscilator (SCO) model, which only accounts for mechanical coupling, has been found to predict adequately the relative intensity of the symmetric and asymmetric bands of dicarbonyl compounds. The dispersion curves predicted for PLLA by the SCO model also match those given by more general treatments, such as Miyazawa's first-order perturbation theory. Hence, the SCO model is adopted here as an adequate yet simple tool for the interpretation of band splitting caused by intramolecular coupling of polylactide. The four components observed in the C=O stretching band of semicrystalline PLLA are attributed to the four possible conformers: gt, gg, tt, and tg. The narrow bands observed for the interlamellar material are attributed to highly ordered chains, indicating the absence of a truly amorphous phase in the crystalline polymer. The interphase seems to extend over the whole interlamellar region, showing the features of a semiordered metastable phase. In amorphous PLLA, bands corresponding to gt, gg, and tt conformers also can be resolved by second derivative techniques, and curve-fitting results provide information about the conformational population at different temperatures.