Engineering of keratin functionality for the realization of bendable all-biopolymeric micro-electrode array as humidity sensor.

The technological quest for flexible devices to be interfaced with the biological world has driven the recent reinvention of bioderived polymers as multifunctional active and passive constituent elements for electronic and photonic devices to use in the biomedical field. Keratin is one of the most important structural proteins in nature to be used as biomaterial platform in view of the recently reported advances in the extraction and processing from hair and wool fibers. In this article we report for the first time the simultaneous use of naturally extracted keratin as both active ionic electrolyte for water ions sensing and as bendable and insoluble substrate into the same multielectrode array-based device. We implemented the multifunctional system exclusively made by keratin as a bendable sensor for monitoring the humidity flow. The enhancement of the functional and structural properties of keratin such as bendability and insolubility were obtained by unprecedented selective chemical doping. The mechanisms at the basis of the sensing of humidity in the device were investigated by cyclic voltammetry and rationalized by reversible binding and extraction of water ions from the volume of the keratin active layer, while the figures of merit of the biopolymer such as the ionic conductivity and relaxation time were determined by means of electrical impedance and dielectric relaxation spectroscopy. A reliable linear correlation between the controlled-humidity level and the amperometric output signal together with the assessment on measure variance are demonstrated. Collectively, the fine-tuned ionic-electrical characterization and the validation in controlled conditions of the free-standing insoluble all-keratin made microelectrode array ionic sensor pave the way for the effective use of keratin biopolymer in wearable or edible electronics where conformability, reliability and biocompatibility are key-enabling features.

Keratins extracted from Merino wool and Brown Alpaca fibres: thermal, mechanical and biological properties of PLLA based biocomposites.

Keratins extracted from Merino wool (KM) and Brown Alpaca fibres (KA) by sulphitolysis and commercial hydrolyzed keratins (KH) were used as fillers in poly(l-lactic) acid based biocomposites processed by solvent casting in chloroform. Different contents (1 wt.% and 5 wt.%) of keratins were considered and the morphological, thermal, mechanical, chemical and biological behaviours of the developed PLLA biocomposites were investigated. The results confirmed that surface morphologies of biocomposites revealed specific round-like surface topography function of different microsized keratin particles in different weight contents, such as the analysis of bulk morphologies which confirmed a phase adhesion strictly dependent by the keratin source. Transparency and thermal responses were deeply affected by the presence of the different keratins and their interaction with the PLLA matrix. Tensile test results underlined the possibility to modulate the mechanical behaviour of PLLA selecting the keratin type and content in order to influence positively the elastic and/or plastic response. It was demonstrated that surface characteristics of PLLA/KA systems also influenced the bovine serum albumin adsorption, moreover PLLA and PLLA biocomposites based on different kinds of keratins supported the culture of human bone-marrow mesenchymal stem cells, indicating that these biocomposites could be useful materials for medical applications.

Study of Methylene Blue adsorption on keratin nanofibrous membranes.

In this work, keratin nanofibrous membranes (mean diameter of about 220nm) were prepared by electrospinning and tested as adsorbents for Methylene Blue through batch adsorption tests. The adsorption capacity of the membranes was evaluated as a function of initial dye concentration, pH, adsorbent dosage, time and temperature. The adsorption capacity increased with increasing the initial dye concentration and pH, while it decreased with increasing the adsorbent dosage and temperature, indicating an exothermic process. The adsorption results indicated that the Langmuir isotherm fitted the experimental data better than the Freundlich and Temkin isotherm models. A mean free energy evaluated through the Dubinin-Radushkevich model of about 16kJmol(-1), indicated a chemisorption process which occurred by ion exchange. The kinetic data were found to fit the pseudo-second-order model better than the pseudo-first-order model. The obtained results suggest that keratin nanofibrous membranes could be promising candidates as dye adsorption filters.

Study on the structure and properties of wool keratin regenerated from formic acid.

Structural characteristics of keratin regenerated from water (KW) and from formic (KF) acid solutions were compared. Amino acid composition and molecular weight distribution of KW and KF samples were studied by high performance liquid chromatography (HPLC) and SDS-PAGE electrophoresis. Turbidity measurement showed that keratin dissolved in formic acid forms transparent and stable solutions and no flocculation occurs. In addition, because of its good solvation properties, studied by viscosity measurements, formic acid can be used as a co-solvent to prepare keratin-based blend solutions. Structural studies carried out by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) and near infrared (NIR) suggest that formic acid stabilizes the beta-sheet structure. Thermogravimetric analysis (TGA) reveals a higher thermal stability of keratin regenerated from formic acid with respect to keratin regenerated from water.