Multifunctional polymeric coatings containing drug delivery vehicles can play a key role in preventing/reducing biofilm formation on implant surfaces. Their requirements are biocompatibility, good adhesion, and controllable drug release. Although cellulose acetate (CA) films and membranes are widely studied for scaffolding, their applications as a protective coating and drug delivery vehicle for metal implants are scarce. The reason is that adhesion to stainless steel (SS) substrates is non-trivial. Grinding SS substrates enhances the adhesion of dip-coated CA films while the adhesion of electrospun CA membranes is improved by an electrosprayed chitosan intermediate layer. PMMA microcapsules containing daptomycin have been successfully incorporated into CA films and fibres. The released drug concentration of 3 x10-3 mg/mL after 120 minutes was confirmed from the peak luminescence intensity under UV radiation of simulated body fluid (SBF) after immersion of the fibres.

Design, research, and development of new and improved smart multifunctional devices is one of the main topics in the advanced functional materials agenda for the next decade. Smart materials that can be triggered by external stimuli are seen with high potential for innovative treatments and improved drug delivery systems by regulatory agencies like the FDA and EMA. The incorporation of magnetic nanostructures into complex systems produces multifunctional devices that can be spatiotemporally controlled by an external magnetic field. These magneto-responsive devices can be used for a multitude of biomedical applications, from diagnostic to the treatment of tumors, and are actively being developed and tested for cancer theranostics. Herein, we review the development of magneto-responsive devices for cancer theranostics, starting from the most straightforward architecture, single nanoparticles. We give some theoretical concepts about the design and production of such systems while providing a critical review of applications in clinical practice. Naturally, the review evolves to more complex architectures, from one-dimensional to three-dimensional magneto-responsive systems, demonstrating higher complexity and multifunctionality, and consequently, higher interest for clinical practice. The review ends with the main challenges in the design and engineering of magneto-responsive devices for cancer theranostics and future trends in this biomedical field.

Electronic controlled drug release from fibres was studied using ibuprofen as a model drug, one of the most popular analgesics, to impregnate gauze and cellulose acetate (CA) membranes. Conductivity in the range of 1–10 mS cm−1 was obtained in polypyrrole (Ppy) functionalised gauze and CA fibres, providing voltage-controlled drug release in a system consisting of Ppy/Ibuprofen/Ppy membranes and an Ag electrode. SEM images evidenced the Ppy adhesion to fibres and Micro Raman spectra proved drug incorporation and release. A small wound adhesive built with these membranes retains ibuprofen at 1.5 V and quickly releases it when −0.5 V is applied.

The present paper regards the preparation and characterization of Pluronic F127 + F68/water/poly (ε-caprolactone) microcapsules (MCs) composite systems for tissue repair. The first part of the work relates to the production of poly(ε-caprolactone) (PCL) MCs via water-in-oil-in-water (W/O/W) double emulsion system combined with solvent evaporation method. The study of different process parameters in the final MCs characteristics and their drug release profile is herein reported. Different percentages of PCL, emulsion stabilizer, and volume proportions of the emulsion constituents have been tested, leading to considerable differences in the MCs size distributions. The selected MCs, containing an aqueous solution of methylene blue (MB) as a model drug, were then used to fill a Pluronic F127 + F68/water system leading to the final composite system (5 and 10 wt % MB loaded PCL MCs). The composite systems were characterised in the second part of the work in terms of its rheological behaviour and drug release performance. They were found to gellify at 30 °C, and present an extended drug release to a total of 18 days. The models that best define the release profiles were also studied, with the release of MB occurring mostly by Fick diffusion and polymer chain relaxation. Pluronic F127 + F68/water/poly (ε-caprolactone) MCs composite system is shown to be a promising injectable system, with two different drug release rates, for tissue repair.

Flexible and stretchable energy-storage batteries and supercapacitors suitable for wearable electronics are at the forefront of the emerging field of intelligent textiles. In this context, the work here presented reports on the development of a symmetrical wire-based supercapacitor able to use the wearer’s sweat as the electrolyte. The inner and outer electrodes consists of a carbon-based thread functionalized with a conductive polymer (polypyrrole) which improves the electrochemical performances of the supercapacitor. The inner electrode is coated with electrospun cellulose acetate fibres, as the separator, and the outer electrode is twisted around it. The electrochemical performances of carbon-based supercapacitors were analyzed using a simulated sweat solution and displayed a specific capacitance of 2.3 F.g−1, an energy of 386.5 mWh.kg−1 and a power density of 46.4 kW.kg−1. Moreover, cycle stability and bendability studies were performed. Such energy conversion device has exhibited a stable electrochemical performance under mechanical deformation, over than 1000 cycles, which make it attractive for wearable electronics. Finally, four devices were tested by combining two supercapacitors in series with two in parallel demonstrating the ability to power a LED.

In this work, eco-friendly magnesium-silicide (Mg2Si) semiconducting (n-type) thermoelectric pastes for building components concerning energy-harvesting devices through 3D printing, spray and electrospinning were synthetized and tested for the first time. The Mg2Si fine powders were obtained through the combination of ball milling and thermal annealing under Ar atmosphere. While the latter process was crucial for obtaining the desired Mg2Si phase, the ball milling was indispensable for homogenizing and reducing the grain size of the powders. The synthetized Mg2Si powders exhibited a large Seebeck coefficient of ~ 487 µV/K and were blended with a polymeric solution in different mass ratios to adjust the paste viscosity to the different requirements of 3D printing, electrospinning and low-pressure spray. The materials produced in every single stage of the paste synthesis were characterized by a variety of techniques that unequivocally prove their viability for producing thermoelectric parts and components. These can certainly trigger further research and development in green thermoelectric generators (TEGs) capable of adopting any form or shape with enhanced thermoelectric properties. These green TEGs are meant to compete with common toxic materials such as Bi2Te3, PbTe and CoSb that have Seebeck coefficients in the range of ~ 290–700 μV/K, similar to that of the produced Mg2Si powders and lower than that of 3D printed bulk Mg2Si pieces, measured to be ~ 4866 μV/K. Also, their measured thermal conductivities proved to be significantly lower (~ 0.2 W/mK) than that reported for Mg2Si (≥ 4 W/mK). However, it is herein demonstrated that such thermoelectric properties are not stable over time. Pressureless sintering proved to be indispensable, but difficultly achievable by long thermal annealing (even above 32 h) in inert atmosphere at 400 °C, at least for bulk Mg2Si pieces constituted by a mean grain size of 2–3 μm. Hence, for overcoming this sintering challenge and become the silicide’s extrusion viable in the production of bulk thermoelectric parts, alternative pressureless sintering methods will have to be further explored.

A novel cellulose-based bio-battery made of electrospun fibers activated by biological fluids has been developed. This work reports a new concept for a fully organic bio-battery that takes advantage of the high surface to volume ratio achieved by an electrospun matrix composed of sub-micrometric fibers that acts simultaneously as the separator and the support of the electrodes. Polymer composites of polypyrrole (PPy) and polyaniline (PANI) with cellulose acetate (CA) electrospun matrix were produced by in situ chemical oxidation of pyrrole and aniline on the CA fibers. The structure (CA/PPy|CA|CA/PANI) generated a power density of 1.7 mW g−1 in the presence of simulated biological fluids, which is a new and significant contribution to the domain of medical batteries and fully organic devices for biomedical applications.

In the present work composite membranes were produced by combining magnetic nanoparticles (NPs) with cellulose acetate (CA) membranes for magnetic hyperthermia applications. The non-woven CA membranes were produced by electrospinning technique, and magnetic NPs were incorporated by adsorption at fibers surface or by addition to the electrospinning solution. Therefore, different designs of composite membranes were obtained. Superparamagnetic NPs synthesized by chemical precipitation were stabilized either with oleic acid (OA) or dimercaptosuccinic acid (DMSA) to obtain stable suspensions at physiological pH. The incorporation of magnetic NP into CA matrix was confirmed by scanning and transmission electron microscopy. The results showed that adsorption of magnetic NPs at fibers’ surface originates composite membranes with higher heating ability than those produced by incorporation of magnetic NPs inside the fibers. However, adsorption of magnetic NPs at fibers’ surface can cause cytotoxicity depending on the NPs concentration. Tensile tests demonstrated a reinforcement effect caused by the incorporation of magnetic NPs in the non-woven membrane.

In this paper the rheological characterization of Pluronic/water systems filled with alginate microparticles is presented. The rheological characterization of the Pluronic/water systems allowed for the choice of the best Pluronic concentration taking into account its applications as injectable hydrogels for tissue repair. The effect on the rheological behavior of the addition of alginate microparticles, to be loaded with the drug, was analyzed and the maximum concentration of microparticles determined.

The unique properties of electrospun nanofibers combined with functional compounds allow the preparation of novelty materials that can be employed in a wide range of applications. Among a vast number of polymers, Cellulose Acetate (CA) it is considered easy to electrospun and it was employed as the polymeric matrix, where free and iridium-porphyrins were incorporated. Two different solvent systems were employed according to the porphyrin used, and the best dispersion level on both the electrospun solution and the membranes, was achieved with the iridium porphyrin. The nanofibers with this porphyrin also exhibited electrical properties, while the fluorescence was quenched by the presence of specific axial ligands.

Fast-dissolving delivery systems (FDDS) have received increasing attention in the last years. Oral drug delivery is still the preferred route for the administration of pharmaceutical ingredients. Nevertheless, some patients, e.g. children or elderly people, have difficulties in swallowing solid tablets. In this work, gelatin membranes were produced by electrospinning, containing an encapsulated therapeutic deep-eutectic solvent (THEDES) composed by choline chloride/mandelic acid, in a 1:2 molar ratio. A gelatin solution (30% w/v) with 2% (v/v) of THEDES was used to produce electrospun fibers and the experimental parameters were optimized. Due to the high surface area of polymer fibers, this type of construct has wide applicability. With no cytotoxicity effect, and showing a fast-dissolving release profile in PBS, the gelatin fibers with encapsulated THEDES seem to have promising applications in the development of new drug delivery systems.

Bone grafting and surgical interventions related with orthopaedic disorders consist in a big business, generating large revenues worldwide every year. There is a need to replace the biomaterials that currently still dominate this market, i.e., autografts and allografts, due to their disadvantages, such as limited availability, need for additional surgeries and diseases transmission possibilities. The most promising replacement materials are biomaterials with bioactive properties, such as the calcium phosphate-based bioceramics group. The bioactivity of these materials, i.e., the rate at which they promote the growth and directly bond with the new host biological bone, can be enhanced through their electrical polarization.
In the present work, the electrical polarization features of pure hydroxyapatite (Hap), pure β-tricalcium phosphate (β-TCP) and biphasic hydroxyapatite/β-tricalcium phosphate composites (HTCP) were analyzed by measuring thermally stimulated depolarization currents (TSDC). The samples were thermoelectrically polarized at 500 °C under a DC electric field with a magnitude of 5 kV/cm. The biphasic samples were also polarized under electric fields with different magnitudes: 2, 3, 4 and 5 kV/cm. Additionally, the depolarization processes detected in the TSDC measurements were correlated with dielectric relaxation processes observed in impedance spectroscopy (IS) measurements.
The results indicate that the β-TCP crystalline phase has a considerable higher ability to store electrical charge compared with the Hap phase. This indicates that it has a suitable composition and structure for ionic conduction and establishment of a large electric charge density, providing great potential for orthopaedic applications.

The strategy of confining stimuli-responsive microgels in electrospun fibres would allow the fabrication of polymeric networks that combine the microgels swelling ability and properties with the interest features of the electrospun fibres. Colloidal electrospinning is an emerging method in which fibres containing microgels can be produced by a single-nozzle and designed through the solution carrier materials. The incorporation of poly(N-isopropylacrylamide) (PNIPAAM) and PNIPAAM-chitosan (PNIPAAM-CS) in poly(ethyleneoxyde) (PEO) fibres via colloidal electrospinning producing composite fibres was the main purpose of the present work{,} which was confirmed by means of Scanning Electron Microscopy (SEM). Dynamic light scattering was used to analyse the microgels hydrodynamic diameter ranging up to 900 nm depending on the composition and temperature of the surrounding medium. By performing a statistical analysis the relationship of the processing variables over the fibre size was evaluated following the response surface methodology (RSM). From the set of parameters aimed to minimize the fibre diameter{,} composite fibres with an average diameter of 63 nm were produced. Only the as-prepared microgels with higher monodispersity provided {"}bead-on-a-string{"} morphologies.

Chitosan is a biopolymer widely used for biomedical applications such as drug delivery systems, wound healing, and tissue engineering. Chitosan can be used as coating for other types of materials such as iron oxide nanoparticles, improving its biocompatibility while extending its range of applications.
In this work iron oxide nanoparticles (Fe3O4 NPs) produced by chemical precipitation and thermal decomposition and coated with chitosan with different molecular weights were studied. Basic characterization on bare and chitosan-Fe3O4 NPs was performed demonstrating that chitosan does not affect the crystallinity, chemical composition, and superparamagnetic properties of the Fe3O4 NPs, and also the incorporation of Fe3O4 NPs into chitosan nanoparticles increases the later hydrodynamic diameter without compromising its physical and chemical properties. The nano-composite was tested for magnetic hyperthermia by applying an alternating current magnetic field to the samples demonstrating that the heating ability of the Fe3O4 NPs was not significantly affected by chitosan.

Composite ferrogels were obtained by encapsulation of magnetic nanoparticles at two different concentrations (2.0 and 5.0 % w/v) within mixed agarose/chitosan hydrogels having different concentrations of agarose (1.0, 1.5 and 2.0% (w/v)) and a fixed concentration of chitosan (0.5% (w/v)). The morphological characterization carried out by scanning electron microscopy showed that dried composite ferrogels present pore sizes in the micrometer range. Thermogravimetric measurements showed that ferrogels present higher degradation temperatures than blank chitosan/agarose hydrogels without magnetic nanoparticles. In addition, measurements of the elastic moduli of the composite ferrogels evidenced that the presence of magnetic nanoparticles in the starting aqueous solutions prevents to some extent the agarose gelation achieved by simply cooling chitosan/agarose aqueous solutions. Finally, it is shown that composite chitosan/agarose ferrogels are able to heat in response to the application of an alternating magnetic field so that they can be considered as potential biomaterials to be employed in magnetic hyperthermia treatments.

The influence of Ag nanoparticles (Ag NPs) on the luminescence of electrospun nonwoven mats made of polyvinylpyrrolidone (PVP) has been studied in this work. The PVP fibers incorporating 2.1–4.3 nm size Ag NPs show a significant photoluminescence (PL) band between 580 and 640 nm under 325 nm laser excitation. The down conversion luminescence emission is present even after several hours of laser excitation, which denotes the durability and stability of fibers to consecutive excitations. As so these one-dimensional photonic fibers made using cheap methods is of great importance for organic optoelectronic applications, fluorescent clothing or counterfeiting labels.

Functionalized electrospun fibers are of great interest for biomedical applications such as in the design of drug delivery systems. Nevertheless, in some cases the molecules of interest have poor solubility in water or have high melting temperatures. These drawbacks can be overcome using deep eutectic solvents. In this work, poly(vinyl alcohol) (PVA), a common biodegradable biopolymer, was used to produce new functionalized fibers with the eutectic mixture choline chloride:citric acid in a molar ratio of (1:1) ChCl:CA (1:1), which was used as a model system. Fibers were produced from an aqueous solution with 7.8% (w/v) and 9.8% (w/v) of 95% hydrolyzed PVA and a 2% (v/v) of ChCl:CA (1:1). Smooth, uniform fibers with an average diameter of 0.4 μm were obtained with a content of 19.8 wt % of ChCl:CA (1:1) encapsulated.

The thermally stimulated discharge current, the final thermally stimulated discharge current, DC conductivity and the final thermally stimulated discharge current with partially blocking electrode measures were used to analyze electrical behavior of Nylon 11. The objective was to discriminate between dipole related effects and space charge related effects. The space charge effects are dominant in the temperature range from room temperature to 170 °C. By using a Teflon-FEP partially blocking electrode, the space charge injected in the sample is diminished and the effects related to dipole movement can be observed. Beside the two known relaxations for Nylon 11, one associated with the glass transition around 60 °C and a second one associated with a molecular motion in the rigid-amorphous phase at 96 °C, a weak relaxation was observed around 168 °C. The peak around 96 °C is quite broad been composed of two narrow peaks. The final thermally stimulated discharge current method allows a better selection of the experimental conditions for sample charging (polarization) to have only a partial overlap between the nearby peaks. The peak's maximum current and temperature are dependent on the ratio between the charging and discharging time and temperature given a possibility to discriminate between dipolar and space charge effects. A pyroelectric current changes sign around 140 °C indicating that the amidegroup dipoles are frozen in opposite directions when the sample temperature is below 140 °C (amorphous and rigid-amorphous phase) or above (crystalline phase). The conductivity is controlled by the competition between n(E,T) and μ(E,T) indicating a space charge controlled conductivity mechanism.

We report a method to obtain electrospun fibers based on ionic liquids and gelatin, exhibiting antimicrobial properties.

Electrospun fibers of poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-bithiophene] (F8T2) with exceptional electro-optical performance are obtained. The I/T characteristics measured in fibers with 7–15 µm diameter and 1 mm length show a semiconductor behavior; their thermal activation energy is 0.5 eV and the dark conductivity at RT is 5 × 10−9 (Ω cm)−1. Besides exhibiting a photosensitivity of about 60 under white light illumination with a light power intensity of 25 mW · cm−2, the fibers also attain RT photoluminescence in the cyan, yellow, and red wavelength range under ultraviolet, blue, and green light excitation, respectively. Optical microscope images of F8T2 reveal homogeneous electrospun fibers, which are in good agreement with the uniformly radial fluorescence observed.

The present work proposes the development of a bio-battery composed by an ultrathin monolithic structure of an electrospun cellulose acetate membrane, over which was deposited metallic thin film electrodes by thermal evaporation on both surfaces. The electrochemical characterization of the bio-batteries was performed under simulated body fluids like sweat and blood plasma [salt solution–0.9% (w/w) NaCl]. Reversible electrochemical reactions were detected through the cellulose acetate structure. Thus, a stable electrochemical behavior was achieved for a bio-battery with silver and aluminum thin films as electrodes. This device exhibits the ability to supply a power density higher than 3 muW cm(-2). Finally, a bio-battery prototype was tested on a sweated skin, demonstrating the potential of applicability of this bio-device as a micropower source.

The objective of this work was to prepare polysaccharide-based gels exhibiting liquid crystalline properties. Such systems may be used in some optical or in biomedical applications, where biodegradability is required. Chitosan is a derivative of chitin, widely used in a series of medical applications. Due to its rigid structure, chitosan or its derivatives may show lyotropic mesophases in certain conditions. In this work, chitosan solutions were prepared by mixing completely the polysaccharide with different concentration of formic, acetic and monochloroacetic acids at room temperature. X-ray diffraction patterns of the gels did not show the existence of a crystalline structure. Finger-prints texture observed by polarised optical microscopy was attributed to a cholesteric liquid crystalline phase that usually develops in concentrated solutions. Values of the nematic chiral pitch (P) were determined in function of acid solution concentration. The critical concentrations (C*) to form a lyotropic liquid crystalline phase in formic, acetic and monochloroacetic acids were determined, and the obtained values were confronted with the expected critical concentration based on the Flory formalism. The critical concentration values were found to be dependent upon the acid used.

The tensile properties of cross-linked and uncross-linked composite films (thickness ∼20–35 μm) prepared from Hydroxypropylcellulose (HPC) with incorporation of microcrystalline cellulose fibers (Avicel) were studied. The concentration of fibers in the composites ranged from 0 to 30 w/w% and cross-linked composites were obtained by the reaction of HPC-Avicel mixtures with 1,4-butyldiisocyanate. It was demonstrated that the inclusion of fibers in a HPC matrix produces composites with enhanced mechanical properties that are improved by cross-linking. Mechanical results seem to indicate that the elastic deformation of the cross-linked composites is predominantly dominated by the fiber content while the cross-linking affects mainly the plastic deformation. Maximum values of the Young's Modulus, yield stress and tensile stress were observed at 10 w/w% for the cross-linked and 20 w/w% for the uncross-linked composites. Furthermore cross-linked films with 10 w/w% of fibers present values of yield stress and tensile stress that are in average 15 to 20% higher than those obtained for uncross-linked composites with 20 w/w% of fibers. Studies in Polarizing Optical Microscopy and Atomic Force Microscopy (AFM) seem to indicate that tensile properties of these composites are correlated to the packing of fibers. For the concentration of the utilized cross-linking agent, and for a fiber content of 10 w/w%, an optimal packing of fibers throughout the matrix has been correlated to the minimal difference between the roughness parameters obtained by AFM analysis of the top and bottom surfaces of the films.

The mechanical and optical properties of cellulose-based composite films are investigated.It is shown that the use of toluene diisocyanate as a coupling agent and Avicel fibers as reinforcing elements give films with the highest mechanical characteristics. Using differential scanning calorimetry, it is also found that the glass transition temperature Tg of all the materials studied is below the room temperature and that the Tg increased with cross-linking and introduction of Avicel.

The present work deals with the preparation and the characterisation of solid films, having thickness between 15 and 40 μm, prepared with hydroxypropyl cellulose (HPC) and different amounts of commercial cellulose fibres (0; 0.5; 10 and 15% w/w) (system A) and with 1,4-butyl diisocyanate (BDI), as a cross-linking agent (system B). Before the preparation of these films, the surface energy of cellulose fibres, as such and after purification with different solvents, was determined by Inverse Gas Chromatography (IGC), which gave the values of dispersive energy and acid-base properties of their surfaces. The tensile and photo-elastic properties of the solid films obtained were studied. There were no significant changes in Young's modulus between the two systems. However, as expected, the values of the elongation and those of the fracture stress were systematically higher for system B in comparison with system A. The same trend was found for the birefringence, measured at the same elongation values for the films obtained from both systems.

A novel liquid-crystalline polymer, the toluene-4-sulphonyl urethane of hydroxypropylcellulose (TSUHPC), was prepared through chemical modification of hydroxypropylcellulose (HPC) of Mw = 60000 g mol−1. The resulting polymer was characterized by infrared spectroscopy, differential scanning calorimetry (DSC) and polarizing microscopy. It was found that thermotropic liquid crystal phases are formed between about 60°C and 110°C. Concentrated solutions of TSUHPC in acetone and N,N-dimethylacetamide exhibit cholesteric behaviour, at room temperature. When approaching the lyotropic mesophase to solid transition, either by cooling or by solvent evaporation, very interesting arborescent structures of a seemingly fractal nature may be observed, depending on the kinetics of the transition. A banded texture can be observed when the polymer is sheared near the transition to the isotropic phase.