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Biodegradation of polyesters driven by enzymes is considered as one of the most effective way of degradation of these materials, as a way to control plastics accumulation in the environment. In this study, we present two different strategies to tune the enzymatic degradation of PBS films triggered by a lipase from Pseudomonas cepacia. Firstly, the kinetics of enzymatic degradation of PBS films was regulated by applying multilayer coats of polysaccharide alginate and chitosan (Alg/Chi) films. Secondly, self-degradable PBS films were prepared by embedding lipase-filled alginate particles. For comparison purposes, a detailed enzymatic degradation study of neat PBS films exposed to a lipase from P. cepacia in solution was made to determine the main experimental parameters influencing their degradation in solution. The results showed that an increase in enzyme concentration increased the degradation extent and rate of neat PBS films. At a fixed enzyme concentration, stirring of the solution containing the enzyme and the PBS also increased the biodegradation rate. In the case of the PBS films coated with a different number of Alg/Chi layers by spray-assisted LbL and subjected to enzymatic degradation experiments in solution, the extent of degradation was found to be dependent on the number of protective coating layers. Therefore, the Alg/Chi biobased coating constitutes an effective barrier to the diffusion of the lipase, thus proving its effectiveness in modulating the enzymatic activity as a function of coating thickness. In the case of self-degradable PBS containing lipase-embedded alginate beads (employed to protect the enzyme during high-temperature processing), only limited biodegradation was observed as the amount of encapsulated enzyme employed was too small. Nonetheless, these results are promising, as the enzymatic activity –indicative of the degradation capacity of the enzyme– determined for all these samples was about 2 orders of magnitude lower than that of p, Peer Reviewed, Objectius de Desenvolupament Sostenible::12 - Producció i Consum Responsables, Postprint (published version)

Diblock copolymers (PPDLx-b-pPAAy) were prepared from ¿-pentadecalactone and l-glutamic acid or l-lysine amino acids by ring opening polymerization initiated by amino groups. Telechelic amino-ended poly(¿-pentadecalactone) with a length of 15–20 repeating units was firstly synthesized by enzymatic polymerization by means of CALB and then used as macroinitiator for the polymerization of the N-carboxyanhydrides of the two a-amino acids conveniently protected as benzyl and eN-carbobenzoxy derivatives, respectively. The molecular weight of the polypeptide block was accurately controlled by adjusting the amino acid/macroinitiator ratio used in the feed. Copolymers with Mn ranging between ~5000 and ~40,000¿g·mol-1 and varying ester/peptide ratio were obtained and characterized in detail by GPC and NMR spectroscopy. The thermal properties of these copolymers were evaluated by TGA and DSC, and their structure in the solid-state including their response to heating, were examined by FTIR and XRD at variable temperature. It was shown that the polypentadecalactone segment was crystallized for all compositions and that the polypeptide counterpart adopted a two-dimensional hexagonal packing of a-helices at temperatures above melting of the polyester block. SAXS revealed the presence of a biphasic nanostructure with a repeating distance of 27¿nm for the case of glutamic-based copolymers. It was demonstrated that both glutamic and lysine-based PPDLx-b-pPAAy copolymers could self-assemble in well-shaped nanospheres with a diameter in the ~200–400¿nm range and a negative zeta-potential, Peer Reviewed, Postprint (author's final draft)

Robust and flexible free-standing films made of spin-coated poly(lactic acid) (PLA) and poly(3,4-ethylenedioxythiophene) (PEDOT) nanolayers have been prepared. A steel sheet coated with a sacrificial layer of PEDOT:poly(styrenesulfonate) (PSS) and a spin-coated nanolayer of PLA was used as working electrode for the anodic polymerization of 3,4-ethylenedioxythiophene monomer. The latter was only successfully accomplished when rounded-shape nanoperforations of average diameter 49¿±¿14¿nm were introduced into PLA layers, which was achieved by combining the phase segregation processes undergone by immiscible PLA:poly(vinyl alcohol) (PVA) mixtures with selective solvent etching to remove PVA domains. Nanoperforations allowed the utilization of the semiconducting PEDOT:PSS sacrificial layer to immobilize the electropolymerized PEDOT chains. Morphological and topographical studies show the templating effect of PEDOT layers. In addition of flexibility and mechanical strength, free-standing 5-layered films present good electrochemical activity, evidencing their potential ability to reversibly exchange ions with the medium. These properties offer important advantages with respect to those of neat PLA and supported PEDOT films, as has been illustrated by cell culture and protein adsorption assays. Cell cultures evidenced the superior behavior of 5-layered films as bioactive platforms for fibroblast and epithelial cells proliferation, while adsorption assays reflected their potential as selective bioadhesive surfaces for protein separation, Peer Reviewed, Postprint (author's final draft)

The preparation of cyclic ethylene and butylene 2,5-furandicarboxylate oligoesters and their conversion to furan-based polyesters poly(ethylene furanoate) (PEF) and poly(butylene furanoate) (PBF) by ring-opening polymerization (ROP) are described. The cyclic oligoesters were obtained in high yields by both high dilution condensation and thermal cyclodepolymerization methods, and they consisted of mixtures of small size species. Cyclic dimer, trimer and tetramer oligoesters were isolated by semipreparative chromatography and found to be crystalline compounds melting within the 140–200 °C range. ROP catalyzed by Sn(Oct)2 of both mixtures and individual species afforded PEF and PBF with weight-average molecular weights between 50,000 and 60,000 g mol-1. Polymerization rate was found to be higher for butylene than for ethylene cyclic oligofuranoates, and also to increase slightly as cycle size decreased. The thermal properties of PEF and PBF prepared by ROP were in full agreement with those reported for these polyesters obtained by melt polycondensation., Peer Reviewed, Postprint (author's final draft)

Electrospun scaffolds from an amino acid containing poly(ester urea) (PEU) were developed as promising materials in the biomedical field and specifically in tissue engineering applications. The selected poly(ester urea) was obtained with a high yield and molecular weight by reaction of phosgene with a bis(alpha-aminoacy1)-alpha,omega-dioldiester monomer. The polymer having L-Ieucine, 1,6-hexanediol and carbonic acid units had a semicrystalline character and relatively high glass transition and melting temperatures. Furthermore it was highly soluble in most organic solvents, an interesting feature that facilitated the electrospinning process and the effective incorporation of drugs with bactericidal activity (e.g. biguanide derivatives such as clorhexidine and polyhexamethylenebiguanide) and enzymes (e.g. alpha-chymotrypsin) that accelerated the degradation process. Continuous micro/nanofibers were obtained under a wide range of processing conditions, being diameters of electrospun fibers dependent on the drug and solvent used.; Poly(ester urea) samples were degradable in media containing lipases and proteinases but the degradation rate was highly dependent on the surface area, being specifically greater for scaffolds with respect to films. The high hydrophobicity of new scaffolds had repercussions on enzymatic degradability since different weight loss rates were found depending on how samples were exposed to the medium (e.g. forced or non-forced immersion). New scaffolds were biocompatible, as demonstrated by adhesion and proliferation assays performed with fibroblast and epithelial cells. (C) 2014 Elsevier B.V. All rights reserved., Peer Reviewed, Postprint (published version)