Annalisa Aluigi

Electrospun Porous Mats for High Efficiency Filtration

Submicron size fibers (so-called nanofibers) are easily produced with an electrospinning apparatus from polymer solutions of poly(ethylene oxide), poly(vinyl alcohol), and polyamide-6. Electrospinning seems the most powerful tool for fabricating polymer nanofibers. Fibers were directly deposited in the form of random fiber webs with high area-to-volume ratio and small porous size on ordinary nonwoven filters of PET microfibers. Morphology and diameter distribution of the electrospun filaments were characterized by SEM investigations. The flow resistance of the produced composite filters are evaluated by means of air permeability measurements. The electrospun fibers have diameters ranging from about 70—500 nm and are interconnected each other to form thin webs that have very small pore size. After the electrospinning treatment, the air permeability of the filter media decreases 6—17 times showing a significant change of flow resistance that can be controlled by the thickness of nanofibers layer and the pore size. High efficiency nano-microfibers composite filters could be used in a wide range of applications, ranging from air cleaning for automotive to environment conditioning or liquid filtration.

Study on Cast Membranes and Electrospun Nanofibers Made from Keratin/Fibroin Blends

Keratin regenerated from wool and fibroin regenerated from silk were mixed in different proportions using formic acid as the common solvent. Both solutions were cast to obtain films and electrospun to produce nanofibers. Scanning electron microscopy investigation showed that, for all electrospun blends (except for 100% keratin where bead defects are present), the fiber diameter of the mats ranged from 900 (pure fibroin) to 160 nm (pure keratin). FTIR and DSC analysis showed that the secondary structure of the proteins was influenced by the blend ratios and the process used (casting or electrospinning). Prevalence of beta-sheet supramolecular structures was observed in the films, while proteins assembled in alpha-helix/random coil structures were observed in nanofibers. Higher solution viscosity, thinner filaments, and differences in the thermal and structural properties were observed for the 50/50 blend because of the enhanced interactions between the proteins.

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.

Morphological and structural investigation of wool-derived keratin nanofibres crosslinked by thermal treatment

Mats of wool-derived keratin nanofibre have been prepared by electrospinning solutions of keratin in formic acid at 20 and 15 wt.%, and obtaining nanofibres with mean diameter of about 400 and 250 nm, respectively. These mats can find applications in tissue engineering (they can mimic the native extracellular matrix) and in wastewater treatment (they can trap small particles and adsorb heavy-metals). A drawback to overcome is their solubility in water. A stabilization method, based on a thermal treatment alternative to the use of formaldehyde, is proposed. The solubility test in the dithiothreitol/urea extraction buffer, the amino acid composition analysis and studies on keratin secondary structures suggest that the improved stability in water of thermally treated mats can be ascribed to the formation of amide bonds between acid and basic groups of some amino acid side chains.

Antibacterial efficacy of polypyrrole in textile applications

This paper describes application and evaluation of polypyrrole as an antibacterial polymer. Polypyrrole was produced embedding two doping agents: chloride and dicyclohexyl sulfosuccinate ions. Stability of the antibacterial efficacy of polypyrrole deposited on cotton fabrics was assessed before and after three different kinds of washing (namely, laundering with anionic and non-ionic detergents and dry-cleaning). Polypyrrole showed excellent antibacterial properties (100 % of bacterial reduction) against Escherichia coli for both doping agents. Treated fabrics were further characterised by scanning electron microscopy, energy dispersive X-ray analysis and infrared spectroscopy. The antibacterial efficacy diminished after launderings with anionic and non-ionic detergents because of two different mechanisms: the neutralisation of positive charges under alkali conditions (dedoping), and a partial removal of polypyrrole by abrasion and surfactant action. After dry-cleaning, polypyrrole embedding chloride and dicyclohexyl sulfosuccinate ions still showed excellent antibacterial efficacy. Moreover, scanning electron microscopy investigations were used to intuitively explain the bactericidal mechanism of polypyrrole on Escherichia coli bacteria.

FT-IR study of dopant-wool interactions during PPy deposition

Coating the fibre surface byin situ oxidative chemical polymerisation of polypyrrole (using FeCl3 as oxidant) is a readily industrial applicable way to give electrical properties to wool with good ageing stability [1], although pre-treatments are required to avoid damage of the cuticle surface due to the acidic condition of the process. FT-IR and EDX analysis reveal that organic sulphonates and sulphates, used as dopants, are absorbed by wool, while chlorine ions are preferably embedded on the polypyrrole layer. The resulting electrical conductivity seems mainly due to the presence of chlorine as counter-ion of polypyrrole; nevertheless, the presence of arylsulphonate in the polymerisation bath increases the electrical conductivity of the coating layer.

Wool-derived keratin nanofiber membranes for dynamic adsorption of heavy-metal ions from aqueous solutions

Membranes made of randomly oriented wool-derived keratin nanofibers (∼240 nm mean diameter), were prepared by electrospinning process, and tested for the Cu(II), Ni(II), and Co(II) metal ion removal from aqueous solutions, through dynamic adsorption tests. The Cu(II) ion adsorption was studied from the isotherm and kinetic point of view, both in non-competitive and competitive conditions. As regards the non-competitive condition, the experimental data had a very good fit with both Langmuir and Freundlich isotherm models. The maximum adsorption capacity obtained from the Langmuir model was about 11 mg/g and the high correlation coefficient of the BET model indicates that the adsorption was a multilayer process. The mean free energy of adsorption, evaluated through the Dubinin–Radushkevich model, was 14.1 kJ/mol, indicating that the adsorption of Cu(II) ions on keratin nanofiber membranes occurred by ion exchange reactions. The process kinetics was evaluated by pseudo-first and pseudo-second order models, the latter showing the highest correlation with the experimental data. The competitive adsorption tests evidenced that the keratin nanofiber membranes maintained a good adsorption capacity for Cu(II) ions and also with the coexistence of Co(II) and Ni(II) metal cations. As regards the selectivity studies, the results showed that the adsorption of metal ions by keratin nanofiber membranes followed the order Cu(II) > Ni(II) > Co(II).

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.

Regenerated keratin membrane to match the in vitro drug diffusion through human epidermis

This work aimed to develop membranes made of regenerated keratin and ceramides (CERs) to match the barrier property of the human stratum corneum in in vitro percutaneous absorption studies. The membrane composition was optimized on the basis of the in vitro drug diffusion profiles of ibuprofen, propranolol and testosterone chosen as model drugs on the basis of their different diffusion and solubility properties. The data were compared to those obtained using human epidermis. The ATR-FTIR and SEM analyses revealed that CERs were suspended into the regenerated keratin matrix, even if a partial solubilization occurred. It resulted in the membranes being physically stable after exposure to aqueous buffer and/or mineral oil and the fluxes of ibuprofen and propranolol from these vehicles through membranes and human skin were of the same order of magnitude. The best relationship with human epidermis data was obtained with 180 μm-thick membrane containing 1% ceramide III and 1% ceramide VI. The data on the testosterone diffusion were affected by the exposure of the membrane to a water/ethanol solution over a prolonged period of time, indicating that such an organic solvent was able to modify the supermolecular organization of keratin and CERs. The keratin/CER membranes can represent a simplified model to assay the in vitro skin permeability study of small molecules.

Microwave-assisted chemical-free hydrolysis of wool keratin

Wool fibers were submitted to “green hydrolysis” with superheated water in a microwave reactor, in view of the potential exploitation of keratin-based industrial and stock-farming wastes. The liquid fraction was separated by filtration from the solid fraction, which consists mainly of small fragments of wool fibers and other insoluble protein aggregates. The liquid fraction contains free amino acids, peptides and low molecular weight proteins, with a small amount of cystine and lanthionine, and has a different secondary structure when compared with keratins extracted from wool via reductive or oxidative methods. Cleavage of the cystine disulfide bonds without the use of harmful, often toxic, reductive or oxidative agents allows the extraction of protein material from keratin wastes, offering the possibility of larger exploitation and valorization.