Ernesto Di Maio

Design of Bimodal PCL and PCL-HA Nanocomposite Scaffolds by Two Step Depressurization During Solid-state Supercritical CO2 Foaming

This communication reports the design and fabrication of porous scaffolds of poly(ε-caprolactone) (PCL) and PCL loaded with hydroxyapatite (HA) nanoparticles with bimodal pore size distributions by a two step depressurization solid-state supercritical CO(2) (scCO(2) ) foaming process. Results show that the pore structure features of the scaffolds are strongly affected by the thermal history of the starting polymeric materials and by the depressurization profile. In particular, PCL and PCL-HA nanocomposite scaffolds with bimodal and uniform pore size distributions are fabricated by quenching molten samples in liquid N(2) , solubilizing the scCO(2) at 37 °C and 20 MPa, and further releasing the blowing agent in two steps: (1) from 20 to 10 MPa at a slow depressurization rate, and (2) from 10 MPa to the ambient pressure at a fast depressurization rate. The biocompatibility of the bimodal scaffolds is finally evaluated by the in vitro culture of human mesenchymal stem cells (MSCs), in order to assess their potential for tissue engineering applications.

Design of novel three-phase PCL/TZ-HA biomaterials for use in bone regeneration applications

The design of bioactive scaffold materials able to guide cellular processes involved in new-tissue genesis is key determinant in bone tissue engineering. The aim of this study was the design and characterization of novel multi-phase biomaterials to be processed for the fabrication of 3D porous scaffolds able to provide a temporary biocompatible substrate for mesenchymal stem cells (MSCs) adhesion, proliferation and osteogenic differentiation. The biomaterials were prepared by blending poly(ε-caprolactone) (PCL) with thermoplastic zein (TZ), a thermoplastic material obtained by de novo thermoplasticization of zein. Furthermore, to bioactivate the scaffolds, microparticles of osteoconductive hydroxyapatite (HA) were dispersed within the organic phases. Results demonstrated that materials and formulations strongly affected the micro-structural properties and hydrophilicity of the scaffolds and, therefore, had a pivotal role in guiding cell/scaffold interaction. In particular, if compared to neat PCL, PCL–HA composite and PCL/TZ blend, the three-phase PCL/TZ–HA showed improved MSCs adhesion, proliferation and osteogenic differentiation capability, thus demonstrating potential for bone regeneration.

Effect of supramolecular structures on thermoplastic zein-lignin bionanocomposites.

The effect of alkaline lignin (AL) and sodium lignosulfonate (LSS) on the structure of thermoplastic zein (TPZ) was studied. Protein structural changes and the nature of the physical interaction between lignin and zein were investigated by means of X-ray diffraction and Fourier transform infrared (FT-IR) spectroscopy and correlated with physical properties. Most relevant protein structural changes were observed at low AL concentration, where strong H-bondings between the functional groups of AL and the amino acids in zein induced a destructuring of inter- and intramolecular interactions in α-helix, β-sheet, and β-turn secondary structures. This destructuring allowed for an extensive protein conformational modification which, in turn, resulted in a strong improvement of the physical properties of the bionanocomposite.

Foaming of Synthetic and Natural Biodegradable Polymers

Biodegradable polymers, both synthetic and natural, often show poor foamability, in terms of the ability to form a fine-celled structure and to retain it. In fact, foams with high density and/or non uniform morphology are generally obtained with these materials. Poor rheological properties, poor solubility and inadequate diffusivity of the ordinary foaming agents, and insufficient setting mechanisms (e.g., crystallization kinetics), are the possible reasons. In this work different approaches, tuned to the different materials, have been investigated to improve the foamability of biodegradable materials, such as polyesters, polysaccharides, vegetal and animal proteins. This comprehensive analysis allows one to gain a wide and clear picture of the relevance and efficiency of the available strategies: process optimization, macromolecular design, choice of blowing agent, and use of additives.

Microstructure, degradation and in vitro MG63 cells interactions of a new poly(ε-caprolactone), zein, and hydroxyapatite composite for bone tissue engineering

Novel biodegradable biomaterials were investigated for potential application in bone tissue engineering. The biomaterials were prepared by blending poly(ε-caprolactone) and thermoplastic zein, a corn protein, with or without the incorporation of hydroxyapatite particles. The biomaterials were characterized in vitro to assess the degradation in phosphate buffer saline for 56 days by monitoring weight change, morphology, wettability, and tensile properties. The interaction between the biomaterials and MG63 was evaluated by proliferation, morphological characterization, and osteogenic differentiation assays up to 28 days in in vitro cultures. The incorporation of thermoplastic zein within poly(ε-caprolactone) enhanced the hydrophilicity and degradability, while minor effects were observed after the inclusion of the hydroxyapatite particles. Compared to the neat poly(ε-caprolactone), the multiphase poly(ε-caprolactone)/thermoplastic zein–hydroxyapatite composite improved the osteogenic differentiation of MG63 cells and is being considered a candidate material for bone tissue engineering applications.

Process-structure Relationships in PCL Foaming

The foaming behavior of poly(ε-caprolactone) (PCL) with nitrogen as the foaming agent has been investigated. By using a uniquely designed and instrumented batch foaming apparatus it is possible to study the correlation between the foam structure (i.e., foam density and mean cell diameter) and the main processing variables (i.e., foaming temperature, foaming agent concentration, and pressure drop rate). A narrow experimental range has been used to describe the complex dependencies by a simple model. In particular, linear algebraic functions have been used to describe the effect of the processing variables on both the foam density and the mean cell diameter. With the aim to better depict these relationships, 3D graphs are also reported. This visualization/ parametrization allows the rapid selection of the proper process parameters to obtain PCL foams with the desired density and morphology.

Heterogeneous bubble nucleation in PCL/clay nanocomposite foams

Abstract Nanocomposites based on biodegradable polycaprolactone (PCL) and organically modified layered silicates (organoclay) have been prepared by melt mixing. The isothermal crystallisation of polycaprolactone/clay nanocomposites showed that the well-dispersed organoclay platelets acted as nucleating agents in the PCL matrix, as confirmed by a remarkable reduction of the crystallisation half-time t1/2. The nanocomposites showed much higher complex viscosity than that of the neat PCL and pseudosolid-like behaviour in the low frequency range. The foaming process of PCL/clay nanocomposites containing 2%wt and 5%wt of clay were investigated by using a batch process. The results showed that the presence of clay resulted in an increase in cell density and a reduction of cell size compared to pure PCL and higher densities due to the higher viscosity of the melt.

Effect of two kinds of lignins, alkaline lignin and sodium lignosulfonate, on the foamability of thermoplastic zein-based bionanocomposites

The aim of this study was to utilize zein, a protein from corn, to develop bioplastic formulations in combination with reactive additives based on ligninic compounds and to investigate the effects of these highly interactive additives on the foamability of zein. In particular, different amounts of alkaline lignin and sodium lignosulfonate were added to zein powder and poly(ethylene glycol) through melt mixing to achieve thermoplastic bio-polymers, which were subsequently foamed in a batch process, with a mixture of CO2 and N2 as blowing agent, in the temperature range 50–60°C. The materials before foaming were characterized by X-ray and Fourier transform infrared analysis to highlight the physico-chemical interactions and the eventual destructuration of the protein secondary structure. After foaming, density measurements, scanning electron microscopy and image analysis have been used in order to evaluate the porosity and the pore size distribution of the microstructure of the foams and to determine the effect of the ligninic compounds on the foamability of the bioplastic.

Hollow micro- and nano-particles by gas foaming

This paper presents the results of a first successful attempt to produce hollow micro- and nano-particles of a large variety of materials, dimensions, shapes and hollow attributes by using an environmentally friendly and cheap technology, common in polymer processing and known as gas foaming. The central role played by ad hoc polymeric hollow micro- and nano-particles in a variety of emerging applications such as drug delivery, medical imaging, advanced materials, as well as in fundamental studies in nanotechnology highlights the wide relevance of the proposed method. Our key contribution to overcome the physical lower bound in the micro- and nano-scale gas foaming was to embed, prior to foaming, bulk micro- and nano-particles in a removable and deformable barrier film, whose role is to prevent the loss of the blowing agent, which is otherwise too fast to allow bubble formation. Furthermore, the barrier film allows for non-isotropic deformation of the particle and/or of the hollow, affording non-spherical hollow particles. In comparison with available methods to produce hollow micro- and nano-particles, our method is versatile since it offers independent control over the dimensions, material and shape of the particles, and the number, shape and open/closed features of the hollows. We have gasfoamed polystyrene and poly-(lactic-co-glycolic) acid particles 200 μm to 200 nm in size, spherical, ellipsoidal and discoidal in shape, obtaining open or closed, single or multiple, variable in size hollows.

Preparation and Characterization of Polyurethane Porous Membranes by Particulate-leaching Method

Highly porous polyurethane foams were prepared by the particulate-leaching technique, using NaCl as water-soluble solid phase. Melt compounding and compression moulding were used to prepare polymer/salt composite samples. Foams with controlled porosity, surface/volume ratio and pore dimension distribution were therefore obtained after dissolution of salt in distilled water. Dissolution kinetic was evaluated and modelled as a function of filler composition and its size distribution. Kinetic increased by rising salt concentration and by reducing its average size. Mechanical properties of the foams were correlated to their morphological structure and to the properties of polymeric component.