Martina Roso

Electrospun scaffolds of self-assembling peptides with poly(ethylene oxide) for bone tissue engineering

Structural, mechanical and biochemical properties have to be considered when searching for suitable extracellular matrix substitutes. Fibrous structures of synthetic or natural polymers have received increasing interest as three-dimensional scaffolds for tissue engineering applications as they can be easily produced by electrospinning with different topographical features by changing the process parameters. On the other hand, the nanobiotechnology approach suggests mimicking molecular architectures in nature through self-assembly. In particular, self-assembling peptide-based biomaterials have been successfully used as scaffolds for cell growth. In order to amalgamate these two strategies nanofibrous electrospun scaffolds of hybrid polymer were designed and obtained by mixing poly(ethylene oxide) and self-assembling peptides in aqueous solution. The results of in vitro osteoblast adhesion and proliferation assays on the electrospun scaffolds obtained using different self-assembling peptide sequences are discussed.

Self-assembling peptide-enriched electrospun polycaprolactone scaffolds promote the h-osteoblast adhesion and modulate differentiation-associated gene expression

Electrospun polycaprolactone (PCL) is able to support the adhesion and growth of h-osteoblasts and to delay their degradation rate to a greater extent with respect to other polyesters. The drawbacks linked to its employment in regenerative medicine arise from its hydrophobic nature and the lack of biochemical signals linked to it. This work reports on the attempt to add five different self-assembling (SA) peptides to PCL solutions before electrospinning. The hybrid scaffolds obtained had regular fibers (SEM analysis) whose diameters were similar to those of the extracellular matrix, more stable hydrophilic (contact angle measurement) surfaces, and an amorphous phase constrained by peptides (DSC analysis). They appeared to have a notable capacity to promote the h-osteoblast adhesion and differentiation process by increasing the gene expression of alkaline phosphatase, bone sialoprotein, and osteopontin. Adding an Arg-Gly-Asp (RGD) motif to a self-assembling sequence was found to enhance cell adhesion, while the same motif condensed with a scrambled sequence did not, indicating that there is a cooperative effect between RGD and 3D architecture created by the self-assembling peptides. The study demonstrates that self-assembling peptide scaffolds are still able to promote beneficial effects on h-osteoblasts even after they have been included in electrospun polycaprolactone. The possibility of linking biochemical messages to self-assembling peptides could lead the way to a 3D decoration of fibrous scaffolds.

Electrospun Scaffolds for Osteoblast Cells: Peptide-Induced Concentration-Dependent Improvements of Polycaprolactone

The design of hybrid poly-ε-caprolactone (PCL)-self-assembling peptides (SAPs) matrices represents a simple method for the surface functionalization of synthetic scaffolds, which is essential for cell compatibility. This study investigates the influence of increasing concentrations (2.5%, 5%, 10% and 15% w/w SAP compared to PCL) of three different SAPs on the physico-chemical/mechanical and biological properties of PCL fibers. We demonstrated that physico-chemical surface characteristics were slightly improved at increasing SAP concentrations: the fiber diameter increased; surface wettability increased with the first SAP addition (2.5%) and slightly less for the following ones; SAP-surface density increased but no change in the conformation was registered. These results could allow engineering matrices with structural characteristics and desired wettability according to the needs and the cell system used. The biological and mechanical characteristics of these scaffolds showed a particular trend at increasing SAP concentrations suggesting a prevailing correlation between cell behavior and mechanical features of the matrices. As compared with bare PCL, SAP enrichment increased the number of metabolic active h-osteoblast cells, fostered the expression of specific osteoblast-related mRNA transcripts, and guided calcium deposition, revealing the potential application of PCL-SAP scaffolds for the maintenance of osteoblast phenotype.

Application of empirical modelling in multi-layers membrane manufacturing

Abstract Multistructured membranes based on ultrafine fibers of polymethylmethacrylate-co-methacrylic acid (PMMA-co-MAA) and TiO2 nanoparticles have been obtained by electrohydrodynamic (EHD) technologies, for active filter media manufacturing. Process optimization of the nanofibers based layers has been investigated by response surface methodology (RSM) in order to predict the domain of the parameters where the smallest fiber diameter can be achieved. A quantitative relationship between electrospinning parameters and the responses (mean diameter and standard deviation) was established and then the final multi-layers structure of nanofibers and nanoparticles has been achieved for a controlled and robust process. The nanostructured membranes have been characterized by SEM imaging, EDAX, TGA analysis and water vapour permeability and their photocatalytic activity has been tested on VOCs degradation.

Characterization of porosity, structure, and mechanical properties of electrospun SiOC fiber mats

In this study, silicon oxycarbide (SiOC) ceramic fiber mats obtained by electrospinning of two different preceramic polymers (MK and H44 resin) were evaluated in terms of their total porosity and other structural characteristics using three different characterization tools. The tensile strength and the permeability of the fiber mats were also investigated. The results indicated that the porosity could be easily calculated based on the apparent density and true density of the fiber mats obtained by gas pycnometry. A modified mercury intrusion porosimetry, in which the bulk volume of the fiber mats was calculated based on its independently measured bulk density, also allowed for an accurate evaluation of the porosity and the pore size distribution of the fiber mats. X-ray computed tomography was able to provide various structural characteristics of the 3D morphology of the fiber mats, but it was less effective in the determination of the total porosity due to resolution limits. All results showed that the MK-derived SiOC fiber mats possessed a higher porosity than the H44-derived SiOC fiber mats, resulting in a higher gas permeability. The ceramic fiber mats possessed a suitable permeability for filtration applications in harsh environments.

Electrically Conductive Membranes Obtained by Simultaneous Electrospinning and Electrospraying Processes

Electrically conductive polyurethane nanostructured membranes have been prepared combining the electrospinning of polymer nanofibers NFs with the electrospraying of pristine multiwall carbon nanotubes MWCNTs in simultaneous processes. In order to have a better understanding of the distribution of MWCNTs on the surface of the membranes, the optimization of the electrospraying process has been carried out and the distribution of MWCNTs has been evaluated using image texture analysis techniques. Large membranes with a volume resistivity typical of electrostatic discharge materials with a MWCNTs concentration less than 0.3% wt 0.01 mg/cm2 have been obtained and characterized with morphological SEM and TEM and spectroscopic UV-Vis, Raman techniques.

Synthesis and Process Optimization of Electrospun PEEK-Sulfonated Nanofibers by Response Surface Methodology

In this study electrospun nanofibers of partially sulfonated polyether ether ketone have been produced as a preliminary step for a possible development of composite proton exchange membranes for fuel cells. Response surface methodology has been employed for the modelling and optimization of the electrospinning process, using a Box-Behnken design. The investigation, based on a second order polynomial model, has been focused on the analysis of the effect of both process (voltage, tip-to-collector distance, flow rate) and material (sulfonation degree) variables on the mean fiber diameter. The final model has been verified by a series of statistical tests on the residuals and validated by a comparison procedure of samples at different sulfonation degrees, realized according to optimized conditions, for the production of homogeneous thin nanofibers.

Facile and selective covalent grafting of an RGD-peptide to electrospun scaffolds improves HUVEC adhesion

The development of a biomimetic surface able to promote endothelialization is fundamental in the search for blood vessel substitutes that prevent the formation of thrombi or hyperplasia. This study aims at investigating the effect of functionalization of poly‐ε‐caprolactone or poly(L‐lactic acid‐co‐ɛ‐caprolactone) electrospun scaffolds with a photoreactive adhesive peptide. The designed peptide sequence contains four Gly‐Arg‐Gly‐Asp‐Ser‐Pro motifs per chain and a p‐azido‐Phe residue at each terminus. Different peptide densities on the scaffold surface were obtained by simply modifying the peptide concentration used in pretreatment of the scaffold before UV irradiation.

Electrospun Nanofibrous Membranes

Membranes comprised of randomly oriented fibers ranging from microns to nanometers in diameter combine small pore size with high porosity. This porous structure has been shown to improve performance in many applications including filtration, catalysis, sensing and tissue engineering. The open porous structure of nanofiber membranes plays an essential role in enhancing the performance of the nanofiber-based materials in these applications. The porous structure of nanofiber membranes is also a determining factor in biological sensors, which require wicking of liquid analytes through the membrane to the detection point. The usage of electrospun nanofibrous scaffolds for biomedical applications has attracted a great deal of attention in the past several years. For examples, nanofibrous scaffolds have been demonstrated as suitable substrates for tissue engineering, immobilized enzymes and catalyst, wound dressing and artificial blood vessels. They have also been used as barriers for the prevention of postoperative induced adhesion and vehicles for controlled drug delivery [1]. For example, tumortargeting nano-scale carrier from electrospun PLGA membranes through surface modification can convey the radio-active nuclide quantitatively to the tumor tissue by directly embedded at the lesions and can also play an anti-adhesion function at where surgical procedures have been made [2]. Nanofiber membranes are ideal for this application because the highly porous network of interconnected pores provides the necessary pathways for transport of oxygen and nutrients that are crucial for cellular growth, and tissue regeneration [3].

Microwave-assisted synthesis of isosorbide-derived diols for the preparation of thermally stable thermoplastic polyurethane

Abstract In order to prepare thermally stable isosorbide-derived thermoplastic polyurethane, the synthesis of two new chiral exo–exo configured diols, prepared from isosorbide, and two types of diphenols (bisphenol A and thiodiphenol) was described. The synthesis conditions were optimized under conventional heating and microwave irradiations. To prove their suitability in polymerization, these monomers were successfully polymerized using 4,4′-diphenylmethane diisocyanate (MDI) and hexamethylene diisocyanate (HDI). Both monomers and polymers have been studied by NMR, FT-IR, TGA, DSC; intrinsic viscosity of polymers has also been determined. The results showed the effectiveness of the synthetic strategy proposed; moreover, a dramatic reduction of the reaction time and an important improvement of the monomers yield using microwave irradiation have been demonstrated. The monomers, as well as the polymers, showed excellent thermal stability both in air and nitrogen. It was also shown that the introduction of sulphur in the polyurethane backbone was effective in delaying the onset of degradation as well as the degradation rate.