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Enzymatic one-pot synthesis procedures in a one-step and two-step monomers addition were developed to obtain poly(glycerol adipate) macromers with methacrylate end-functional groups under the presence of 1 and 3 wt% of Candida antarctica lipase B (CALB). Glycerol, divinyl adipate, and vinyl methacrylate were enzymatically reacted (vinyl methacrylate was either present from the beginning in the monomers solution or slowly dropped after 6 h of reaction) in tetrahydrofuran (THF) at 40 °C over 48 h. Macromers with a methacrylate end groups fraction of ≈52% in a simple one-pot one-step procedure were obtained with molecular weights (Mn) of ≈7500–7900 g/mol. The obtained products under the one-pot one-step and two steps synthesis procedures carried out using 1 and 3 wt% of a CALB enzymatic catalyst were profusely characterized by NMR (1H and 13C), MALDI-TOF MS, and SEC. The methacrylate functional macromers obtained with the different procedures and 1 wt% of CALB were combined with an Irgacure® 369 initiator to undergo homopolymerization under UV irradiation for 10 and 30 min, in order to test their potential to obtain amorphous networks within minutes with similar properties to those typically obtained by complex acrylation/methacrylation procedures, which need multiple purification steps and harsh reagents such as acyl chlorides. To the best of our knowledge, this is the first time that it has been demonstrated that the obtention of methacrylate-functional predominantly linear macromers based on poly(glycerol adipate) is able to be UV crosslinked in a simple one-step procedure.

The design and development of multifunctional fibers awakened great interest in biomaterials and food packaging materials. One way to achieve these materials is by incorporating functionalized nanoparticles into matrices obtained by spinning techniques. Here, a procedure for obtaining functionalized silver nanoparticles through a green protocol, using chitosan as a reducing agent, was implemented. These nanoparticles were incorporated into PLA solutions to study the production of multifunctional polymeric fibers by centrifugal force-spinning. Multifunctional PLA-based microfibers were obtained with nanoparticle concentrations varying from 0 to 3.5 wt%. The effect of the incorporation of nanoparticles and the method of preparation of the fibers on the morphology, thermomechanical properties, biodisintegration, and antimicrobial behavior, was investigated. The best balance in terms of thermomechanical behavior was obtained for the lowest amount of nanoparticles, that is 1 wt%. Furthermore, functionalized silver nanoparticles confer antibacterial activity to the PLA fibers, with a percentage of killing bacteria between 65 and 90%. All the samples turned out to be disintegrable under composting conditions. Additionally, the suitability of the centrifugal force-spinning technique for producing shape-memory fiber mats was tested. Results demonstrate that with 2 wt% of nanoparticles a good thermally activated shape-memory effect, with high values of fixity and recovery ratios, is obtained. The results obtained show interesting properties of the nanocomposites to be applied as biomaterials.

In this work, we described the combination of photocurable methacrylic monomer and poly(glycerol adipate) (PGA) macromer to form networks that can be further quaternized to provide antimicrobial character. Both monomers were synthesized enzymatically. Networks with different content of methacrylic monomer were prepared and further characterized by water contact angle measurements, surface charge, soluble fractions, differential scanning calorimetry and microhardness to determine the effect of the methacrylic monomer in the PGA network. Methacrylic monomer affected the mechanical behavior but did not alter the surface wettability, whereas the quaternization did not alter the wettability nor the mechanical properties of the network surfaces. Finally, the obtained network with the introduced permanent cationic charges were tested against Gram-positive S. aureus and Gram-negative E. coli bacteria showing remarkable antimicrobial activity which increased with the content of methacrylic monomer in the network. Moreover, the assays against red blood cells demonstrated that networks are no toxic.

In this work, we described the formation of polymeric networks with potential antimicrobial character based on an acrylate oligomer, poly(mannitol sebacate) (PMS), and an enzymatically synthesized methacrylic monomer with thiazole groups (MTA). Networks with different content of MTA were prepared, and further physico-chemically characterized by microhardness, water contact angle measurements, and differential scanning calorimetry. Monomer incorporation into the networks and subsequent quaternization to provide thiazolium moieties affected the mechanical behavior and the surface wettability of the networks. Moreover, the introduction of permanent cationic charges in the network surface could give antimicrobial activity to them. Therefore, the antibacterial behavior and the hemotoxicity were analyzed against Gram-positive and Gram-negative bacteria and red blood cells, respectively.

The catalytic specificity of Lipase B from Candida antarctica (CALB) has been exploited to achieve specific terminal groups for the synthesis of glycerol poly(ester)s. This permits the preparation of glycerol-derived macromers able to undergo further reactions/chemical modifications for customization as functional systems and building blocks for polymer synthesis. Poly(glycerol adipate) based macromers with different terminal structures were achieved from the reaction between glycerol and divinyl adipate by varying the stoichiometry (from equimolar to 1.5 and 3.0 excess either of glycerol or divinyl adipate) and amount of catalyst (1 and 3 wt%). In the course of polymerization, transesterification and hydrolysis reactions occur over vinyl functionalities that result in acid endgroups. Thus, the resulting macromers are either terminated with hydroxyl groups and/or acid groups and/or vinyl groups. Therefore, an understanding of how acid functionality appears (from vinyl groups hydrolysis) and its quantification under various conditions may provide an opportunity for the design of synthetic strategies to avoid acid production and obtain the desired structures. Endgroup analysis was carried out using H NMR and C NMR spectroscopies and MALDI-TOF spectrometry. Mainly linear hydroxyl and vinyl-terminated macromers were obtained with high efficiency without significant hydrolysis of the chain ends (for vinyl terminated).

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.

This article reviews the most important advances in the enzymatic synthesis of polyesters. In first place, the different processes of polyester enzymatic synthesis, i.e., polycondensation, ring opening, and chemoenzymatic polymerizations, and the key parameters affecting these reactions, such as enzyme, concentration, solvent, or temperature, are analyzed. Then, the latest articles on the preparation of polyesters either by direct synthesis or via modification are commented. Finally, the main bioapplications of enzymatically obtained polyesters, i.e., antimicrobial, drug delivery, or tissue engineering, are described. It is intended to point out the great advantages that enzymatic polymerization present to obtain polymers and the disadvantages found to develop applied materials.

Poly(lactic acid) (PLA) is one of the most commonly employed synthetic biopolymers for facing plastic waste problems. Despite its numerous strengths, its inherent brittleness, low toughness, and thermal stability, as well as a relatively slow crystallization rate represent some limiting properties when packaging is its final intended application. In the present work, silver nanoparticles obtained from a facile and green synthesis method, mediated with chitosan as a reducing and stabilizing agent, have been introduced in the oligomeric lactic acid (OLA) plasticized PLA in order to obtain nanocomposites with enhanced properties to find potential application as antibacterial food packaging materials. In this way, the green character of the matrix and plasticizer was preserved by using an eco-friendly synthesis protocol of the nanofiller. The X-ray diffraction (XRD) and differential scanning calorimetry (DSC) results proved the modification of the crystalline structure as well as the crystallinity of the pristine matrix when chitosan mediated silver nanoparticles (AgCH-NPs) were present. The final effect over the thermal stability, mechanical properties, degradation under composting conditions, and antimicrobial behavior when AgCH-NPs were added to the neat plasticized PLA matrix was also investigated. The obtained results revealed interesting properties of the final nanocomposites to be applied as materials for the targeted application.