Ella Schoolaert

Blend electrospinning of dye-functionalized chitosan and poly(ε-caprolactone): towards biocompatible pH-sensors

Fast-response and easy-to-visualize colorimetric nanofibrous sensors show great potential for visual and continuous control of external stimuli. This makes them applicable in many fields, including wound management, where nanofibers serve as an optimal support material. In this paper, fast responding and user-friendly biocompatible, halochromic nanofibrous sensors are successfully fabricated by incorporating the halochromic dyes Methyl Red and Rose Bengal inside a chitosan/poly(ε-caprolactone) nanofibrous matrix. The commonly applied dye-doping technique frequently suffers from dye-leaching, which not only reduces the sensors sensitivity over time but can also induce adverse effects. Therefore, in this work, dye-immobilization is accomplished by covalent dye-modification of chitosan before blend electrospinning. It is shown that efficient dye-immobilization with minimal dye-leaching is achieved within the biomedical relevant pH-region, without significantly affecting the halochromic behavior of the dyes. This is in contrast to the commonly applied dye-doping technique and other dye-immobilization strategies stated in literature. Moreover, the nanofibers show high and reproducible pH-sensitivity by providing an instantaneous color change in response to change in pH in aqueous medium and when exposed to acidic or basic gases. The results stated within this work are of particular interest for natural (bio)polymers for which covalent modification combined with electrospinning provides a universal method for versatile dye-functionalization of large area nanofibrous membranes with proper dye-immobilization.

Waterborne Electrospinning of Poly(N-isopropylacrylamide) by Control of Environmental Parameters

With increasing toxicity and environmental concerns, electrospinning from water, i.e., waterborne electrospinning, is crucial to further exploit the resulting nanofiber potential. Most water-soluble polymers have the inherent limitation of resulting in water-soluble nanofibers, and a tedious chemical cross-linking step is required to reach stable nanofibers. An interesting alternative route is the use of thermoresponsive polymers, such as poly(N-isopropylacrylamide) (PNIPAM), as they are water-soluble beneath their lower critical solution temperature (LCST) allowing low-temperature electrospinning while the obtained nanofibers are water-stable above the LCST. Moreover, PNIPAM nanofibers show major potential to many application fields, including biomedicine, as they combine the well-known on-off switching behavior of PNIPAM, thanks to its LCST, with the unique properties of nanofibers. In the present work, based on dedicated turbidity and rheological measurements, optimal combinations of polymer concentration, environmental temperature, and relative humidity are identified allowing, for the first time, the production of continuous, bead-free PNIPAM nanofibers electrospun from water. More specifically, PNIPAM gelation was found to occur well below its LCST at higher polymer concentrations leading to a temperature regime where the viscosity significantly increases without compromising the polymer solubility. This opens up the ecological, water-based production of uniform PNIPAM nanofibers that are stable in water at temperatures above PNIPAMs LCST, making them suitable for various applications, including drug delivery and switchable cell culture substrates.

Nanostructured Hydrogels by Blend Electrospinning of Polycaprolactone/Gelatin Nanofibers

Nanofibrous membranes based on polycaprolactone (PCL) have a large potential for use in biomedical applications but are limited by the hydrophobicity of PCL. Blend electrospinning of PCL with other biomedical suited materials, such as gelatin (Gt) allows for the design of better and new materials. This study investigates the possibility of blend electrospinning PCL/Gt nanofibrous membranes which can be used to design a range of novel materials better suited for biomedical applications. The electrospinnability and stability of PCL/Gt blend nanofibers from a non-toxic acid solvent system are investigated. The solvent system developed in this work allows good electrospinnable emulsions for the whole PCL/Gt composition range. Uniform bead-free nanofibers can easily be produced, and the resulting fiber diameter can be tuned by altering the total polymer concentration. Addition of small amounts of water stabilizes the electrospinning emulsions, allowing the electrospinning of large and homogeneous nanofibrous structures over a prolonged period. The resulting blend nanofibrous membranes are analyzed for their composition, morphology, and homogeneity. Cold-gelling experiments on these novel membranes show the possibility of obtaining water-stable PCL/Gt nanofibrous membranes, as well as nanostructured hydrogels reinforced with nanofibers. Both material classes provide a high potential for designing new material applications.