Background
Peri-implantitis is considered the most challenging biological complication in implantology, as untreated disease can progress and result in implant loss. Therefore, disease prevention is crucial in daily clinical practice. It has been reported that the use of bioactive glass, as an implant coating, can stimulate tissue integration and accelerate tissue regeneration. Besides these properties, it is possible to promote bacterial activity by inserting silver into the bioglass

Methods
Bioglass with composition 45S5 was synthesised by the fusion method, replacing the amount of Na2CO3 by AgNO3 (BG 2% wt). The implants were resealed by the CoBlast® technique. Clinical cases with pathology of the mandible/maxilla were selected and implants dimensioned for the canine bone structure were applied.

Results
Three months after implantation, imaging exams, namely CT scans, showed no signs of early rejection by septic or cytotoxic loss. No decrease or loss of peri-implant bone was observed. In all cases the implants remained without signs of instability, and with sufficient support for the application of the exo-prosthesis or dental crown. The results of histological analysis showed no signs of infection or osteolysis. The zone of peri-implant fibrosis was not observable in the samples, showing a good evolution in implant osteointegration.

Conclusions
The results show promising evidences for the use of this biomaterial as a coating, since aseptic rejection, later on, and that related to the shape and biomaterials used in the implant's design, usually begins during the first 3 months.

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 delivery of multiple anti-cancer agents holds great promise for better treatments. The present work focuses on developing multifunctional materials for simultaneous and local combinatory treatment: Chemotherapy and hyperthermia. We first produced hybrid microgels (MG), synthesized by surfactant-free emulsion polymerization, consisting of Poly (N-isopropyl acrylamide) (PNIPAAm), chitosan (40 wt.%), and iron oxide nanoparticles (NPs) (5 wt.%) as the inorganic component. PNIPAAm MGs with a hydrodynamic diameter of about 1 μm (in their swollen state) were successfully synthesized. With the incorporation of chitosan and NPs in PNIPAAm MG, a decrease in MG diameter and swelling capacity was observed, without affecting their thermosensitivity. We then sought to produce biocompatible and mechanically robust membranes containing these dual-responsive MG. To achieve this, MG were incorporated in poly (vinyl pyrrolidone) (PVP) fibers through colloidal electrospinning. The presence of NPs in MG decreases the membrane swelling ratio from 10 to values between 6 and 7, and increases the material stiffness, raising its Young modulus from 20 to 35 MPa. Furthermore, magnetic hyperthermia assay shows that PVP-MG-NP composites perform better than any other formulation, with a temperature variation of about 1 °C. The present work demonstrates the potential of using multifunctional colloidal membranes for magnetic hyperthermia and may in the future be used as an alternative treatment for cancer.

Engineering drug delivery systems (DDS) aim to release bioactive cargo to a specific site within the human body safely and efficiently. Hydrogels have been used as delivery matrices in different studies due to their biocompatibility, biodegradability, and versatility in biomedical purposes. Microparticles have also been used as drug delivery systems for similar reasons. The combination of microparticles and hydrogels in a composite system has been the topic of many research works. These composite systems can be injected in loco as DDS. The hydrogel will serve as a barrier to protect the particles and retard the release of any bioactive cargo within the particles. Additionally, these systems allow different release profiles, where different loads can be released sequentially, thus allowing a synergistic treatment. The reported advantages from several studies of these systems can be of great use in biomedicine for the development of more effective DDS. This review will focus on in situ injectable microparticles in hydrogel composite DDS for biomedical purposes, where a compilation of different studies will be analysed and reported herein.

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.

Cancer remains as one of the major causes of mortality worldwide. Recent advances in nanoparticles based therapy mark a new era on cancer treatment. Many groups have investigated biological/physical effects of nanoparticles on tumour cells and how these vary with physical parameters such as particle size, shape, concentration and distribution. Magnetic hyperthermia (MHT) can be an alternative or an add-value therapy with demonstrated effectiveness. MHT uses magnetic nanoparticles, which can be directly applied to the tumour, where, by applying an external ac magnetic field, will promote a localized temperature increment that can be controlled.

The physical properties of the cubic and ferrimagnetic spinel ferrite LiFe5O8 has made it an attractive material for electronic and medical applications. In this work, LiFe5O8 nanosized crystallites were synthesized by a novel and eco-friendly sol-gel process, by using powder coconut water as a mediated reaction medium. The dried powders were heat-treated (HT) at temperatures between 400 and 1000 °C, and their structure, morphology, electrical and magnetic characteristics, cytotoxicity, and magnetic hyperthermia assays were performed. The heat treatment of the LiFe5O8 powder tunes the crystallite sizes between 50 nm and 200 nm. When increasing the temperature of the HT, secondary phases start to form. The dielectric analysis revealed, at 300 K and 10 kHz, an increase of ε′ (≈10 up to ≈14) with a tanδ almost constant (≈0.3) with the increase of the HT temperature. The cytotoxicity results reveal, for concentrations below 2.5 mg/mL, that all samples have a non-cytotoxicity property. The sample heat-treated at 1000 °C, which revealed hysteresis and magnetic saturation of 73 emu g−1 at 300 K, showed a heating profile adequate for magnetic hyperthermia applications, showing the potential for biomedical applications.

Several problems and limitations faced in the treatment of many diseases can be overcome by using controlled drug delivery systems (DDS), where the active compound is transported to the target site, minimizing undesirable side effects. In situ-forming hydrogels that can be injected as viscous liquids and jellify under physiological conditions and biocompatible clay nanoparticles have been used in DDS development. In this work, polymer–clay composites based on Pluronics (F127 and F68) and nanoclays were developed, aiming at a biocompatible and injectable system for long-term controlled delivery of methylene blue (MB) as a model drug. MB release from the systems produced was carried out at 37 °C in a pH 7.4 medium. The Pluronic formulation selected (F127/F68 18/2 wt.%) displayed a sol/gel transition at approx. 30 °C, needing a 2.5 N force to be injected at 25 °C. The addition of 2 wt.% of Na116 clay decreased the sol/gel transition to 28 °C and significantly enhanced its viscoelastic modulus. The most suitable DDS for long-term application was the Na116-MB hybrid from which, after 15 days, only 3% of the encapsulated MB was released. The system developed in this work proved to be injectable, with a long-term drug delivery profile up to 45 days.

High-entropy alloys (HEAs) have been around since 2004. The breakthroughs in this field led to several potential applications of these alloys as refractory, structural, functional, and biomedical materials. In this work, a short overview on the concept of high-entropy alloys is provided, as well as the theoretical design approach. The special focus of this review concerns one novel class of these alloys: biomedical high-entropy alloys. Here, a literature review on the potential high-entropy alloys for biomedical applications is presented. The characteristics that are required for these alloys to be used in biomedical-oriented applications, namely their mechanical and biocompatibility properties, are discussed and compared to commercially available Ti6Al4V. Different processing routes are also discussed.

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.

Advanced functionalities textiles embedding electronic fibers, yarns and fabrics are a demand for innovative smart cloths. Conductive electrospun membranes and yarns based on polyaniline/polyvinylpyrrolidone (PANI/PVP) were investigated using the chemical modification of PANI instead of using conventional coating processes as in-situ polymerization. PANI was synthesized from the aniline monomer and the influence of the oxidant-to-monomer ratio on electrical conductivity was studied. The optimized conductivity of pellets made with pressed PANI powders was 21 S·cm−1. Yarns were then prepared from the t-Boc-PANI/PVP electrospun membranes followed by PANI protonation to enhance their electrical properties. Using this methodology, electrospun membranes and yarns were produced with electrical conductivities of 1.7 × 10−2 and 4.1 × 10−4 S·cm−1.

We demonstrate a simple and accessible method for enhancing textiles with custom piezo-resistive properties. Based on in-situ polymerization, our method offers seamless integration at the material level, preserving a textile's haptic and mechanical properties. We demonstrate how to enhance a wide set of fabrics and yarns using only readily available tools. During each demo session, conference attendees may bring textile samples which will be polymerized in a shared batch. Attendees may keep these samples. While the polymerization is happening, attendees can inspect pre-made samples and explore how these might be integrated in functional circuits. Examples objects created using polymerization include rapid manufacturing of on-body interfaces, tie-dyed motion-capture clothing, and zippers that act as potentiometers.

Peri-implantitis is an infectious disease that affects about one of five patients who receive a dental implant within 5 years after the surgery. To minimize this reaction the development of new biomaterials with antibacterial action is needed that can be used as a coating material in orthodontic implants. In addition, these biomaterials can be doped with several ions, which add specific properties that may act at the cellular level, such as increasing the angiogenesis efficiency. In this work, 45S5 Bioglass® has been used as the base material because it presents higher bioactivity compared to other biomaterials. To add antibacterial function and increase positive effects on bone metabolism, zinc and magnesium ions were introduced in the glass network. The main objective was the synthesis of the 45S5 glass by melt-quenching and study the biological performance as function of the zinc and magnesium concentrations. The structural and biological properties of the prepared samples are discussed.

Background
The use of 3D printing of hydrogels as a cell support in bio-printing of cartilage, organs and tissue has attracted much research interest. For cartilage applications, hydrogels as soft materials must show some degree of rigidity, which can be achieved by photo- or chemical polymerization. In this work, we combined chemical and UV laser polymeric cross-linkage to control the mechanical properties of 3D printed hydrogel blends. Since there are few studies on UV laser cross-linking combined with 3D printing of hydrogels, the work here reported offered many challenges.

Methods
Polyethylene glycol diacrylate (PEGDA), sodium alginate (SA) and calcium sulphate (CaSO4) polymer paste containing riboflavin (vitamin B2) and triethanolamine (TEOHA) as a biocompatible photoinitiator was printed in an extrusion 3D plotter using a coupled UV laser. The influence of the laser power on the mechanical properties of the printed samples was then examined in unconfined compression stress-strain tests of 1 × 1 × 1 cm3 sized samples. To evaluate the adhesion of the material between printed layers, compression measurements were performed along the parallel and perpendicular directions to the printing lines.

Results
At a laser density of 70 mW/cm2, Young’s modulus was approximately 6 MPa up to a maximum compression of 20% in the elastic regime for both the parallel and perpendicular measurements. These values were within the range of biological cartilage values. Cytotoxicity tests performed with Vero cells confirmed the cytocompatibility.

Conclusions
We printed a partial tracheal model using optimized printing conditions and proved that the materials and methods developed may be useful for printing of organ models to support surgery or even to produce customized tracheal implants, after further optimization.

his paper reports the application of additive manufacturing technology to fabricate bi-dimensional lightweight composite meshes capable of demonstrating auxetic properties (negative Poisson's ratio (NPR)) in combination with negative thermal expansion (NTE) behaviour, using as constituent materials polymers that do not exhibit NTE behaviour. To describe the combination of NPR and NTE characteristics, the designation of 'anepectic' is being proposed. Each mesh, obtained from varying either the material combination or the design parameters, was tested on a heated silicone bath to study the effects of the different combinations on the coefficient of thermal expansion (CTE). It was found that all meshes studied demonstrated a successful combination of NPR and NTE behaviours, and it was revealed that there is a possibility to tailor the meshes to activate the NTE behaviour within a chosen range of temperatures. For an extreme case, a Poisson's ratio of −0.056, along with a CTE of −1568 × 10−6 K−1 has been achieved.

The composition and architecture of a scaffold determine its supportive role in tissue regeneration. In this work, we demonstrate the feasibility of obtaining a porous electrospun fibrous structure from biodegradable polyurethanes (Pus) synthesized using polycaprolactone-diol as soft segment and, as chain extenders, chitosan (CS) and/or dimethylol propionic acid. Fourier transform infrared spectroscopy and proton nuclear magnetic resonance confirmed the syntheses. Fibre mats' properties were analysed and compared with those of solvent cast films. Scanning electron microscopy images of the electrospun scaffolds revealed fibres with diameters around 1 μm. From tensile tests, we found that Young's modulus increases with CS content and is higher for films (2.5 MPa to 6.5 MPa) than for the corresponding fibre mats (0.8 MPa to 3.2 MPa). The use of CS as the only chain extender improves recovery ratio and resilience. From X-ray diffraction, a higher crystalline degree was identified in fibre mats than in the corresponding films. Films' wettability was enhanced by the presence of CS as shown by the decrease of water contact angle. X-ray photoelectron spectroscopy revealed that while ester groups are predominant at the films' surface, ester and urethanes are present in similar concentrations at fibres' surface, favouring the interaction with water molecules. Both films and fibres undergo hydrolytic degradation. In vitro evaluation was performed with human dermal fibroblasts. No PU sample revealed cytotoxicity. Cells adhered to fibre mats better than to films and proliferation was observed only for samples of CS-containing PUs. Results suggest that electrospun fibres of CS-based polyurethanes are good candidate scaffolds for soft tissue engineering.

The aim of the present study is to investigate the effect of the hydrolysis process on the properties of nanocrystalline cellulose (NCC) isolated from different precursors and the subsequent use of the extracted NCC for the reduction of graphene oxide (GO). The raw materials (almond and peanut shells) chosen for the isolation of cellulose were selected on the basis of their abundance and their poorly investigation in the production of NCC. Microcrystalline cellulose (MCC) was firstly extracted by alkali and bleaching treatments, then hydrolyzed under different processes to produce NCC polymorphs with structure I (NCC-I) and NCC structure II (NCC-II). The Fourier transform infrared spectroscopy, the X-ray diffraction (XRD) and the 13C NMR studies of the alkali and bleached products confirmed the formation of cellulose type I with high purity and good crystallinity, while scanning electron microscopy (SEM) showed micrometric fibers with lengths reaching 80 µm. Sulfuric acid treatment of these microfibers results in NCC type I or II, depending on the hydrolysis process. SEM of the NCC samples exhibited nanorods with diameter and aspect ratio in the range of 20–40 and 20–25 nm, respectively. Thermogravimetric analysis (TGA) of the MCC and NCC products indicated stable materials with a degradation temperature reaching 240 and 200 °C for MCC and NCC, respectively. The other part of our work concerns the use of the obtained cellulose nanocrystals (type II) for the preparation of reduced graphene oxide composite (NCC/RGO), to demonstrate the reducing properties of the isolated NCCII.

A (model) composite system for drug delivery was developed based on a thermoresponsive hydrogel loaded with microparticles. We used Pluronic F127 hydrogel as the continuous phase and alginate microparticles as the dispersed phase of this composite system. It is well known that Pluronic F127 forms a gel when added to water in an appropriate concentration and in a certain temperature range. Pluronic F127 hydrogel may be loaded with drug and injected, in its sol state, to act as a drug delivery system in physiological environment. A rheological characterization allowed the most appropriate concentration of Pluronic F127 (15.5 wt%) and appropriate alginate microparticles contents (5 and 10 wt%) to be determined. Methylene blue (MB) was used as model drug to perform drug release studies in MB loaded Pluronic hydrogel and in MB loaded alginate microparticles/Pluronic hydrogel composite system. The latter showed a significantly slower MB release than the former (10 times), suggesting its potential in the development of dual cargo release systems either for drug delivery or tissue engineering.

Bacterial infections affect about 1 in 5 patients who receive a dental implant within 5 years of surgery. To avoid the implant rejection it is necessary for the development of innovative biomaterials, with addition or substitution of the ions, for implant coatings that promote a strong bond with the new host bone and antibacterial action. The objective of this work was to synthesize a bioactive glass with different silver concentrations to evaluate their antibacterial performance. The glasses were synthesized with up to 2% silver content by melt-quenching. Structural, morphological, biological, and electrical properties of all samples were studied. The biological behavior was evaluated through cytotoxicity tests and antibacterial activity. The structural analysis shows that the introduction of silver do not promote significant changes, not altering the advantageous properties of the bioglass of the bioglass. It was verified that the glasses with a silver content from 0.5% to 2%, completely prevented the growth of both Staphylococcus aureus and Escherichia coli while being nontoxic toward mammalian cells. Therefore, these bioglasses are promising materials to be used in the production of dental implants with antimicrobial activity.

Truncated sialylated O-glycans, such as cell-surface carbohydrate antigen sialyl-Tn (STn) are overexpressed by several cancer types, but not by the respective normal tissues. STn expression is associated with oncogenesis and metastatic ability of cancer cells, with reduced overall survival and lack of response to chemotherapy. Advances in nanomedicine have resulted in rapid development of biocompatible superparamagnetic iron oxide nanoparticles (SPIONs) with considerable potential in cancer treatment. Therefore, in this study SPIONs coated with oleic acid (OA) or dimercaptosuccinic acid (DMSA) were developed and characterized for internalization in two breast cancer cell lines: cell line expressing the STn antigen and the corresponding control. SPIONs with an average diameter of 8 nm showed superparamagnetic behavior and high potential to be used as magnetic hyperthermia agents. OA and DMSA coating provided high stability of SPIONs in physiological conditions while not changing their main properties. NPs internalization studies showed a higher accumulation of DMSA coated NPs in the breast cancer MDA-MB-231 WT cell line. In MDA-MB-231 cell line expressing STn both coated NPs showed a similar accumulation. Therefore, STn antigen can act as a receptor capable of detecting and covalently bind to the molecules present on NPs surface and induce their cellular uptake by endocytosis.

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.

Control of the properties of electrospun polycaprolactone can be achieved by adjusting the acetic acid:water ratio used to dissolve and electrospin the polymer. In this work, we studied the effect of using up to 15 wt% water in the solvent mixture. Solution conductivity and viscosity and fibre morphology vary dramatically with water content and solution age. Two days after initial solution preparation, electrospinning yields regular fibres for a water content of 0 wt% and 5 wt%, irregular fibres for a 10 wt% water content and irregular and fused fibres for a 15 wt% water content. Fibres with the highest crystallinity (60%) were obtained from solutions containing 5 wt% water while the highest elastic modulus (8.6 ± 1.4 MPa) and tensile stress (4.3 ± 0.3 MPa) pertain to fibres obtained from solutions containing 10 wt% water. Enzymatic fibre degradation is faster the higher the water content in the precursor solution. Adhesion ratio of human foetal fibroblasts was highest on scaffolds obtained from precursor solutions containing 0 wt% water. Cell population increases for all scaffolds and populations quickly become equivalent, with no statistically significant differences between them. Cells exhibit a more extended morphology on the 5 wt% scaffold and a more compact morphology on the 0 wt% scaffold. In summary, a small water content in the solvent allows a significant control over fibre diameter, scaffold properties and the production of scaffolds that support cell adhesion and proliferation. This strategy can be used in soft tissue engineering to influence cell behaviour and the degradation rate of the scaffolds.

A simple process of commercial paper functionalisation via in situ polymerisation of conductive polymers onto cellulose fibres was investigated and applied as electrodes in paper-based batteries. The functionalisation involved polypyrrole (PPy) and Poly (3,4-ethylenedioxythiophene) (PEDOT) as conductive polymers with the process of functionalisation optimised for each polymer individually with respect to oxidant-to-monomer ratios and polymerisation times and temperature. Paper with conductivity values of 44 mS/cm was obtained by exposing the samples to pyrrole vapour for a period of 30 min at room temperature; however, polymerisation at temperatures of 40 °C lead to higher conductivity values to up 141 mS/cm. Consequently, functionalised PPy and PEDOT papers were applied as cathodes in batteries with Al foil anodes and commercial paper soaked in an electrolyte solution of NaCl.

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.

One strategy that has gained much attention in the last decades is the understanding and further mimicking of structures and behaviours found in nature, as inspiration to develop materials with additional functionalities. This review presents recent advances in stimuli-responsive gels with emphasis on functional hydrogels and microgels. The first part of the review highlights the high impact of stimuli-responsive hydrogels in materials science. From macro to micro scale, the review also collects the most recent studies on the preparation of hybrid polymeric microgels composed of a nanoparticle (able to respond to external stimuli), encapsulated or grown into a stimuli-responsive matrix (microgel). This combination gave rise to interesting multi-responsive functional microgels and paved a new path for the preparation of multi-stimuli “smart” systems. Finally, special attention is focused on a new generation of functional stimuli-responsive polymer hydrogels able to self-shape (shape-memory) and/or self-repair. This last functionality could be considered as the closing loop for smart polymeric gels.

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.

Biodegradable polyurethanes have been studied as scaffolds for tissue engineering due to their adjustable physico-chemical properties. In this work, we synthesized a biodegradable gelatin-based poly(urethane urea) using polycaprolactone-diol, as soft segment, and isophorone diisocyanate and gelatin from cold water fish skin as hard segment. The synthesis was confirmed by Fourier transform infrared spectroscopy and proton nuclear magnetic resonance and the influence of the amount of gelatin introduced in the polymer backbone was analyzed by thermal analysis. Gelatin-based poly(urethane urea) electrospun fibrous mats and solvent cast films were then produced and their physico-chemical and biological properties studied. They present an amorphous structure, elastomeric behavior and water contact angles typical of hydrophobic surfaces. Hydrolytic degradation was analyzed in phosphate buffer saline (PBS), lipase and trypsin solutions. No mass changes were detected during 37 days in PBS and trypsin while significant degradation by lipase was observed. Human foetal foreskin fibroblasts were seeded on the fibrous mats and films. Populations were evaluated by colorimetric cell viability assays and morphology by fluorescence imaging. The substrates supported cell adhesion and proliferation. The novel gelatin-based poly(urethane urea) fibrous mats offer attractive physico-chemical and biological properties for soft tissue engineering applications.

Inspired by chitin based hierarchical structures observed in arthropods exoskeleton, this work reports the capturing of chitin nanowhiskers’ chiral nematic order into a chitosan matrix. For this purpose, highly crystalline chitin nanowhiskers (CTNW) with spindle-like morphology and average aspect ratio of 24.9 were produced by acid hydrolysis of chitin. CTNW were uniformly dispersed at different concentrations in aqueous suspensions. The suspensions liquid crystalline phase domain was determined by rheological measurements and polarized optical microscopy (POM). Chitosan (CS) was added to the CTNW isotropic, biphasic and anisotropic suspensions and the solvent was evaporated to allow films formation. The Films’ morphologies as well as the mechanical properties were explored. A correlation between experimental results and a theoretical model, for layered matrix’ structures with fibers acting as a reinforcement agent, was established. The results evidence the existence of two different layered structures, one formed by chitosan layers induced by the presence of chitin and another formed by chitin nanowhiskers layers. By playing on the ratio chitin/chitosan one layered structure or the other can be obtained allowing the tunning of materials’ mechanical properties.

Chitosan with three different molecular weights (538 ± 48, 229 ± 45 and 13 ± 3 kDa) was used to develop biodegradable Inverted Colloidal Crystal (ICC) scaffolds with uniform pore size and interconnected pore network. Mass loss and compression modulus were analyzed after hydrolytic degradation in order to understand the influence of molecular weight on structural and mechanical degradation of chitosan ICC structures. Results show that medium molecular weight chitosan (229 ± 45 kDa) retains ICC structure and compression modulus for an extended period (4 weeks) and is therefore the preferred one for the production of ICC for soft tissue engineering.

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.

Hybrid materials have been widely studied for structural applications. Polysaccharide-based fibers, especially cellulosic fibers, have been explored in the last two decades as substitutes of the traditional reinforcements made of glass or carbon fibers due to their mechanical properties. However, their biocompatibility, biodegradability, and chemistry have attracted the researchers and new developments in the field of smart and functional materials arise in diverse applications. This chapter will focus on the biomedical applications of polysaccharide-based smart and functional materials, namely those concerning biosensors and actuators, theranostic systems, and tissue-engineering applications. Special attention will be given to cellulose- and chitin/chitosan-based hybrid materials because these are the two most abundant polysaccharides and probably the most promising for the development of hybrid materials for biomedical applications. Biomimetic strategies for the development of smart and functional hybrid materials will also be highlighted.

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.

Nanometric and sub-micrometric monodispersed hydroxyapatite (HAp) particles with different morphologies (spheres and rods) were synthesized via a simple solvothermal method using Ca(NO3)2·4H2O and P2O5 as starting materials without any requirement to use organic templates. The growth, evolution and purity of the nanoparticles were investigated by controlling the synthesis conditions, including the alkalinity and the temperature of the solvothermal treatment. The increasing of the alkaline ratio results in a great change of the elaborated particles’ morphology that evolved from anisotropic forms (nanorods, sub-micrometric rod) at pH 9, short rod particles at pH 9.5 to spherical ones at higher pH (pH≥10).
Powder X-Ray diffractometry (XRD), Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR) and Nitrogen adsorption and desorption studies (BET) were used to characterize the structure and composition of the as-prepared samples.
The thermal analysis of the synthesized particles conducted by differential scanning calorimetry (DSC) shows a good stability for all morphologies with a degradation temperature reaching 1300 °C.

Sub-micrometric Co fibers were prepared via a modified polyol process at 90 °C under an external magnetic field of about 550 Oe, using ethelyne glycol as solvent and hydrazine as reducing agent. The structure, the size and the morphology of the as-elaborated products were highly controlled through properly monitoring the synthesis parameters (amount of NaOH added, the amount of the reducing agent, precursor’ concentration and precursors mixing protocol). The XRD characterization confirmed the formation of pure cobalt powders with either hexagonal compact (hcp) or face-centered-cubic (fcc) structure depending on the concentration of the metal precursor and sodium hydroxide. The scanning electron microscopy observations of the powders shows sub-micrometric fibers with about 0.4–0.6 µm in diameter and a length that could reach 15 µm. Fibers prepared at high reducing ratio were constituted of flower-like spheres that coalesce in the direction of the applied magnetic field. For their high contact surface, these fibers offer new opportunities for catalysis applications. The hysteresis loop measurements show an enhancement of the Hc of the as-obtained fibers compared to their bulk counterparts and permit to confirm the relationship between the structure and the magnetic properties of the materials.

The incorporation of thermosensitive microgels that can act as active sites into polymeric fibers through colloidal electrospinning originates multifunctional, highly porous, and biocompatible membranes suitable for biomedical applications. The use of polyvinylpyrrolidone (PVP), a biocompatible, water-soluble polymer as a fiber template, not only allows the use of a simple set-up to produce composite membranes, but also avoids the use of organic solvents to prepare such systems. Further crosslinking with ultraviolet (UV) radiation avoids membrane dissolution in physiological conditions. Highly porous, UV crosslinked composite membranes with monodisperse mean fiber diameters around 530 nm were successfully produced. These composite membranes showed a Young Modulus of 22 MPa, and an ultimate tensile strength of 3 MPa, accessed in the mechanical tests. Furthermore, the same composite membranes were able to swell about 30 times their weight after 1 hour in aqueous medium. In this work composite multifunctional membranes were designed and extensively studied. PVP, a biocompatible water-soluble polymer, was used as a fiber template to incorporate thermoresponsive poly-(N-isopropylacrylamide) (PNIPAAm)-based microgels into the composite membrane using colloidal electrospinning. The design of multifunctional membranes can be further tailored to several biomedical applications such as temperature-controlled 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.

In the present work, two drug delivery systems were produced by encapsulating doxorubicin into chitosan and O-HTCC (ammonium-quaternary derivative of chitosan) nanoparticles. The results show that doxorubicin release is independent of the molecular weight and is higher at acidic pH (4.5) than at physiological pH. NPs with an average hydrodynamic diameter bellow 200 nm are able to encapsulate up to 70% and 50% of doxorubicin in the case of chitosan and O-HTCC nanoparticles, respectively. O-HTCC nanoparticles led to a higher amount of doxorubicin released than chitosan nanoparticles, for the same experimental conditions, although the release mechanism was not altered. A burst effect occurs within the first hours of release, reaching a plateau after 24 h. Fitting mathematical models to the experimental data led to a concordant release mechanism between most samples, indicating an anomalous or mixed release, which is in agreement with the swelling behavior of chitosan described in the literature.