The Incorporation of Low-Molecular Weight Poly(Mannitol Sebacate)s on PLA Electrospun Fibers: Effects on the Mechanical Properties and Surface Chemistry

Abstract

We offer a report on the synthesis of low-molecular weight biobased poly(mannitol sebacate) (PMS) and its functionalization with acrylate groups (PMSAc). These synthesized polyesters were blended at a low level (10 wt%) with poly (lactic acid) PLA to prepare aligned fibers by electrospinning, coupled with a rotatory collector. The obtained fibers were extensively studied by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and wide-angle X-ray diffraction (WAXS), employing synchrotron radiation. The incorporation of the PMSs on the PLA fibers did not significantly affect the fiber diameters, whereas the alignment was almost maintained. The crystallinity and thermal properties were also slightly modified with the addition of PMSs, and an increase in the degree of crystallinity and in the glass transition temperature of the blend compared to PLA was observed. Remarkably, the PLA/PMSs fibers were more ductile due to the elastomeric character of PMS, with higher values of elongation at break and tensile strengths, and a smaller Young modulus in comparison with the PLA fibers. These modifications of the properties were more noticeable in the case of the acrylated PMS, which also provided readily available functional groups at the surface for further chemical reactions, such as the Michael addition or crosslinking processes.

Photocured Poly(Mannitol Sebacate) with Functional Methacrylic Monomer: Analysis of Physical, Chemical, and Biological Properties

“…The synthesis of a PMS polyester from D-mannitol and sebacic acid and its subsequent functionalization with acrylate groups was successfully performed previously [ 34 ]. These polymers were incorporated into poly(lactic acid) to create functionalized fibers.…”

“…1 H NMR (400 MHz, CDCl 3 , ppm): δ = 8.52 (s, 1H; =CH thiazole), 6.02 (m, 1H; =CH), 5.49 (m, 1H; =CH), 4.22 (t, J = 6.5 Hz, 2H; OCH 2 ), 3.06 (t, J = 6.5 Hz, 2H; CH 2 ), 2.33 (s, 3H; CH 3 thiazole), 1.84 (dd, J = 1.2, 1.5 Hz, 3H; CH 3 ); 13 C NMR (400 MHz, CDCl 3 , ppm): δ = 166.9 (C=O), 149.9 and 149.7 (NCs), 135.9 (–C=CH 2 ), 126.8, 125.8 (=CH 2 s and C=C–S), 64.1, 25.7, 18.3, 14.7. Poly(mannitol sebacate) (PMS) (Mn and Ð obtained by SEC were 2480 g/mol and 1.22, respectively) and PMS-Ac (~80% of functionalization) were also synthesized according to previously published methods [ 34 ]. Briefly, PMS was synthesized from SA and D -mannitol in bulk at 150 °C in a molar ratio SA/MA of 1/1.1.…”

“…In this article, a previously synthesized macromer of acrylated poly(mannitol sebacate) (PMS-Ac) [ 34 ] and enzymatically synthesized 2-(4-methylthiazol-5-yl)ethyl methacrylate (MTA) [ 26 ] were used to obtain different 3D networks by photopolymerization. These networks were modified by alkylation to introduce permanent cationic charges, with the intention of providing antimicrobial character.…”

Effects of blending poly (polyol sebacate) and poly (polyol adipate) bioelastomers for soft tissue engineering in biomedical applications

“…When comparing the mechanical behavior of blends with similar works, it becomes apparent that blending these bioelastomers with their families is a more effective method for adjusting mechanical behavior without compromising other advantages. 17,25,26,33…”

“…Nonetheless, it should be noted that an increase in the percentage of polylactic acid has led to the observation of inflammation in the rat's body. 25,26 Moreover, it has been observed that this particular family of bioelastomers can be combined with minerals, vitamins, and drugs to create suitable composites for drug delivery and tissue engineering applications. 24,[27][28][29][30] Through the blending of poly (glycerol sebacate) with polycaprolactone, it has been demonstrated that it is possible to maintain biocompatibility at a level comparable to pure poly (glycerol sebacate) while also achieving a wide range of mechanical properties.…”