Synthesis and characterization of divinyl-fumarate Poly-ε-caprolactone for scaffolds with controlled architectures

A vinyl-terminated Polycaprolactone has been developed for tissue engineering applications using a one-step synthesis and functionalization method based on Ring Opening Polymerization (ROP) of ԑ-caprolactone, with Hydroxyl Ethyl Vinyl Ether (HEVE) acting both as the initiator of ROP and as photo-curable functional group. The proposed method employs a catalyst based on Al, instead of the most popular Tin(II) 2-ethylhexanoate, to reduce the cytotoxicity. Following the synthesis of the vinyl-terminated polycaprolactone, its reaction with Fumaryl Chloride (FuCl) results in a divinyl-fumarate polycaprolactone (VPCLF). The obtained polymers were thoroughly characterized using Fourier Transform Infrared Spectroscopy (FTIR) and gel permeation chromatography (GPC) techniques. The polymer has been successfully employed, in combination with N-vinyl Pyrrolidone (NVP), to fabricate films and computer-designed porous scaffolds by micro-stereolithography (μ-SL) with Gyroid and Diamond architectures. Characterization of the networks indicated the influence of NVP content on the network properties. Human Mesenchymal Stem Cells (hMSCs) adhered and spread onto VPCLF/NVP networks showing good biological properties and no cytotoxic effect

Three-Dimensional Poly(ε-caprolactone) Bioactive Scaffolds with Controlled Structural and Surface Properties

The requirement of a multifunctional scaffold for tissue engineering capable to offer at the same time tunable structural properties and bioactive interface is still unpaired. Here we present three-dimensional (3D) biodegradable polymeric (PCL) scaffolds with controlled morphology, macro-, micro-, and nano-mechanical performances endowed with bioactive moieties (RGD peptides) at the surface. Such result was obtained by a combination of rapid prototyping (e.g., 3D fiber deposition) and surface treatment approach (aminolysis followed by peptide coupling). By properly designing process conditions, a control over the mechanical and biological performances of the structure was achieved with a capability to tune the value of compressive modulus (in the range of 60–90 MPa, depending on the specific lay-down pattern). The macromechanical behavior of the proposed scaffolds was not affected by surface treatment preserving bulk properties, while a reduction of hardness from 0.50–0.27 GPa to 0.1–0.03 GPa was obtained. The penetration depth of the chemical treatment was determined by nanoindentation measurements and confocal microscopy. The efficacy of both functionalization and the following bioactivation was monitored by analytically quantifying functional groups and/or peptides at the interface. NIH3T3 fibroblast adhesion studies evidenced that cell attachment was improved, suggesting a correct presentation of the peptide. Accordingly, the present work mainly focuses on the effect of the surface modification on the mechanical and functional performances of the scaffolds, also showing a morphological and analytical approach to study the functionalization/bioactivation treatment, the distribution of immobilized ligands, and the biological features