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One of the main issues of wearable electronic devices regards their power supply and autonomy. The exploitation of mechanical energy from body motion and vibrations can be realized by using piezoelectric materials coupled with a proper energy storage device. To this aim, Self-Powered Supercapacitors (SPSCs) have been investigated over the last decades, either as internally integrated SPSC (iSPSC), where the piezoelectric element of the device is used as Super Capacitor (SC) separator, or via an external integration (eSPSC), where the piezoelectric unit and the SC are connected by a bridge rectifier. In this paper, an eSPSC power supply is developed by integrating a stuck of commercial ceramic piezoelectric disks and an ionic liquid-based micro-SC. In detail, a stack of 15 commercial lead zirconate titanate (PZT) disks is used as the energy harvesting unit and mechanically stressed by a compressive force of 85 N at 2 Hz. The piezoelectric output successfully charged the 22 mF supercapacitor up to 3.1 V after 2 h of test, achieving a stored energy value equal to 110 mJ. The proposed integrated system outperforms the state-of-the-art SPSC assembled with micro-SC (both iSPSC and eSPSC). The use of the two different units (piezo-energy harvesting unit and micro-SC energy storage unit) allows an independent sizing and tuning of the supercapacitor according to the output current of the piezoelectric unit.

Simultaneous SAXS-WAXD measurements are carried out to gain information about the microstructure and the molecular orientation developed by polymeric chains during the electrospinning process. Three semicrystalline polymers were studied, namely polyacrylonitrile, Nylon 6,6, and poly(ethylene oxide), as non-woven mats with either randomly arranged or aligned electrospun fibers. Mat thermal and morphological properties are investigated, together with their structural details in order to derive their hierarchical structure from the macro to the nano-scale. SAXS patterns have an elliptical shape with the main axis along the equator direction. No reflections are noticeable along the meridional direction, suggesting that the investigated electrospun fibers have a fibrillar structure with no trace of lamellar morphology. Combining the values of the unit cell and of the crystal size it can be concluded that in the fibers the ordered domains are organized into a bundle of fibrils due to the lateral aggregation of roughly 10 unit cells and the regular ordering of about either 50 (Nylon 6,6 and polyacrylonitrile) or 25 (poly(ethylene oxide)) cells in the chain direction.

In this work Nylon 6,6 nanofibrous mats produced by electrospinning were used as interlayers in carbon fiber reinforced laminates. A high crossilinked epoxy resin was chosen as matrix. The effects of polymeric mats on cure behavior, thermal and delamination properties of the composite laminates were investigated.

In the evolving field of tissue engineering, continuous advances are required to improve scaffold design and fabrication to obtain biomimetic supports for cell adhesion, proliferation, penetration and differentiation. Both electrospun fibrous scaffolds and hydrogels are used in this field since they well reproduce the structure of the extracellular matrix (ECM) of many biological tissues. Limitations of these two types of materials can be overcome through their combination, by developing composite structures combining enhanced mechanical properties (provided by the fibrous components) and improved cell penetration (provided by the gel phase) in a superior ability to mimic natural ECM that is constituted by both a fibrous protein network and a hydrogel matrix. Here we develop new composite materials made of electrospun PLLA scaffolds and poly(amidoamine) hydrogels with different degrees of crosslinking. To promote compatibilization and good adhesion between the two materials, surface chemical reactions between hydrogels and PLLA mats are induced by inserting amino functional groups on electrospun PLLA mats by means of atmospheric pressure non-thermal plasma. Results will be presented concerning the exposure of PLLA substrates to the plasma region generated by a Dielectric Barrier Discharge at atmospheric pressure, driven by a HV Amplifier connected to a function generator operating with a microsecond rise time and operated in N2. Surface and solid-state thermo-mechanical characterizations of plasma treated substrates and of resulting composite materials at different crosslinking degrees are presented. Results of mechanical tests show a high adhesion between hydrogel and plasma treated PLLA electrospun mats, underlining the opportunity to use atmospheric non-thermal plasmas to fabricate a composite starting from two materials otherwise physically incompatible. Potential effects of nanofibrous-hydrogel were evaluated by investigating pluripotent stem cells response.

Nanotechnology is revolutionising the world of materials. The research and development of nanofibres has gained much prominence in recent years due to the heightened awareness of its potential applications in the medical, engineering and defense fields. Among the most successful methods for producing nanofibres is the electrospinning process. Electrospinning introduces a new level of versatility and broader range of materials into the micro/nanofibre range. An old technology, electrospinning has been rediscovered, refined, and expanded into non-textile applications. This book offers an overview of structure - property relationships, synthesis and purification, and potential applications of electrospun nanofibres. The collection of topics aims to reflect the diversity of recent advances in electrospun nanofibers with a broad perspective which may be useful for scientists as well as for graduate students and engineers. The book presents leading-edge research from around the world in this dynamic field. Diverse topics on electrospun Nanofibers published in this book are the original works of some world wide well-known scientists.

The promising trends in biotechnology and tissue engineering are based on the development of advanced materials with biomimetic features in order to recreate the native environment promoting the appropriate cell behavior for tissue regeneration. Cell therapy together with novel functionalized biomaterials represent a very promising approach in regenerative medicine for cartilage regeneration. Articular cartilage exhibits a well-ordered organization with an extracellular matrix arranged as a network of collagen fibers and proteoglycans that allow for cell adhesion, mechanical support, transduction of chemical and mechanical signals from the surrounding tissue to the cells. Electrospun materials are considered highly promising scaffolds for cartilage tissue engineering given their specific fibrous morphology that resembles the fibrous component of tissue extracellular matrix. Many synthetic and natural polymers have been successfully electrospun to obtain scaffolds. Among natural polymers, collagen is universally applied as biomaterial in regenerative medicine because of its unique biocompatibility, and structural property. Robust techniques for surface “biodecoration” are currently required and the appropriate surface functionalization still remains a critical variable for the optimal performance of a wide range of biomaterials. Covalent bonding of bioactive molecules to material surface is a valid strategy in order to allow a sufficiently strong and specific affinity of biomolecules with the surface itself; in addition covalent bonding may permit site-directed immobilization and preservation of specific conformation and exposition to control biological responses. Plasma processes allow to tune surface properties of materials with negligible effect on their bulk. The need of improving cell/surface interaction has decisively introduced plasma techniques in the field of biomaterials; In addition, a wide range of compounds can be chosen as a monomer for plasma polymerization, providing a great diversity of possible surface modifications with different functional groups, including amine, anhydride, epoxide, carboxylic acid, cyano, halide, hydroxyl, furfuryl, and perfluoroalkyl.

De-pulped multilayer packaging waste containing low-density polyethylene (LDPE) and aluminium was separated into its single components by using sustainable solvents capable of solubilizing LDPE under mild conditions. LDPE and aluminium of high purity and quality were recovered with biodiesel, 2-methyl tetrahydrofuran (2-MeTHF) and cyclopentyl methyl ether (CPME). The recovered LDPE has been characterized by thermal and mechanical analysis, confirming its similarity to the polymer before the dissolution process, while the recovered aluminium was analysed by X-Ray Photoelectron Spectroscopy (XPS) depth profiling, confirming the non-oxidative behaviour of the tested solvents. The mass balance of the recovered materials and solvents at the end of the dissolution process was close to 100%

A straightforward way for the preparation of mechanochromic polymers consists of incorporating a suitable content of a mechanophore in the polymeric matrix either by physical dispersion or via covalent functionalization. Although covalent incorporation may require demanding chemical efforts, this approach can offer significant advantages over physical dispersion. In this work, a common thermoplastic elastomer, styrene-b-(ethylene-co-butylene)-b-styrene triblock copolymer grafted with maleic anhydride (SEBS-MAH), was covalently functionalized with 1-aminomethylpyrene (AMP). MAH functional groups are covalently linked to the ethylene-co-butylene blocks, thus allowing a precise and selective confinement of the chromogenic AMP units in the soft block. Flat, fully conjugated pyrene units undergo the reversible formation of pi-pi aggregates, readily distinguishable by their red-shifted emission. These aggregates were heavily affected by the application of mechanical stimuli. Despite the low degree of mechanophore functionalization (about 1 wt %), uniaxial deformation of the polymer was reliably monitored via fluorescence and a clear drop in the excimer to monomer emission ratio (I-E/I-M) was observed starting from 50% of strain. The marked mechanochromism was confirmed by emission lifetime measurements and also by near-field investigations. In addition, the mechanoresponse showed good reversibility after repeated stress-relaxation cycles. Control experiments performed on formulations comprising a physical dispersion of pyrene in unfunctionalized SEBS showed faint excimer emission and a negligible mechanochromic response up to 5 wt % of doping, in substantial agreement with the scanning near-field optical microscopy analysis. An evident drop of the I-E/I-M ratio occurred for 10 wt % of pyrene, albeit the excimer emission remained predominant even at the highest deformation, being a smaller fraction of pyrene moieties involved. Overall, the covalent approach appeared as an elegant procedure to confine the chromogenic unit in the soft phase of block copolymers and thus to provide an elastomeric film showing a detectable and reversible mechanochromic response with a modest (i.e., similar to 1 wt %) amount of pyrene molecules, i.e., 10 times smaller compared to the dispersed system.

The removal of toxic and carcinogenic polycyclic aromatic hydrocarbons (PAHs) from water is one of the most intractable environmental problems nowadays, because of their resistance to remediation. This work introduces a highly efficient, regenerable membrane for the removal of PAHs from water, featuring excellent filter performance and pH-driven release, thanks to the integration of a cavitand receptor in electrospun polyacrylonitrile (PAN) fibers. The role of the cavitand receptor is to act as molecular gripper for the uptake/release of PAHs. To this purpose, the deep cavity cavitand BenzoQxCav is designed and synthetized and its molecular structure is elucidated via X-Ray diffraction. The removal efficiency of the new adsorbent material toward the 16 priority PAHs is demonstrated via GC-MS analyses at ng L-1 concentration. A removal efficiency in the 32%, to 99% range is obtained. The regeneration of the membrane is performed by exploiting the pH-driven conformational switching of the cavitand between the vase form, where the PAHs uptake takes place, to the kite one, where the PAHs release occurs. The absorbance and regeneration capability of the membrane are successfully tested in four uptake/release cycles and the morphological stability.

This paper aims to investigate the energy harvesting capabilities of two piezoelectric nanogenerators based on ceramic and polymeric nanofibers. The nanofibers are produced via electrospinning and assembled with the electrodes to fabricate flexible and wearable devices. The specimens are mechanically stressed at low frequencies and the piezo-current is used to charge a capacitor. The performances of the piezoelectric nanofibers are then compared with those of a commercial ceramic piezoelectric disk.

The terpene-based monomers and polymers reported in the literature are mostly hydrophobic and this is limiting their use in aqueous environments. To address this drawback, we have developed a novel synthetic strategy to functionalise a model terpene monomer in order to improve hydrophilicity and the number of polar groups on the polymer side chains. To produce a highly hydrophilic monomer, carvone (meth)acrylate was chosen as the primary feedstock. Carvone has more functionalisable double bonds than other commercial cyclic terpenes and offers the potential for the maximum number of hydrophilic groups per monomer molecule. The monomers were homopolymerised and copolymerised to generate novel green hydrophilic and amphiphilic terpene-based polymers which were characterised by 1H–13C NMR, gel permeation chromatography, TGA and DSC analyses. © 2020 Society of Industrial Chemistry.

Realizing active, light-emitting fibers made of conjugated polymers by the electrospinning method is generally challenging. Electrospinning of plasma-treated conjugated polymer solutions is here developed for the production of light-emitting microfibers and nanofibers. Active fibers from conjugated polymer solutions rapidly processed by a cold atmospheric argon plasma are electrospun in an effective way, and they show a smoother surface and bead-less morphology, as well as preserved optical properties in terms of absorption, emission, and photoluminescence quantum yield. In addition, the polarization of emitted light and more notably photon waveguiding along the length of individual fibers are remarkably enhanced by electrospinning plasma-treated solutions. These properties come from a synergetic combination of favorable intermolecular coupling in the solutions, increased order of macromolecules on the nanoscale, and resulting fiber morphology. Such findings make the coupling of the electrospinning method and cold atmospheric plasma processing on conjugated polymer solutions a highly promising and possibly general route to generate light-emitting and conductive micro- and nanostructures for organic photonics and electronics.

A novel hyphenated Pyrolysis-Anaerobic Digestion prototype (Py-AD) was tested in order to evaluate the potential of hybrid thermochemical biological process to produce methane from woody biomass. An auger intermediate pyrolyzer was directly coupled to two biological reactors optimized for the digestion of residual condensable compounds and gas produced by pyrolysis of softwood. The Py-AD was monitored for 16 months and a detailed chemical analysis of the main fractions, gas (pyrobiogas), biochar, aqueous phase and pyrolytic lignin was performed under regime conditions. The results from Py-AD and those from experiments with bench-scale pyrolysis and fermentation reactors analysis provided information on the overall performance of the Py-AD and mass and energy balance based on chemical oxygen demand. Py-AD allowed to obtain, with acceptable volumetric productivity, a pyrobiogas with a composition approaching that of biogas (47 %v/v CH4 and 45 %v/v CO2). Pyrobiogas yield was about half of the theoretical value calculated from gas and liquid fractions. A preliminary technical evaluation of the process confirmed the feasibility of Py-AD and its value to produce carbon negative fuels with simple equipment and low waste generation. Important key constraints of the process were also evidenced in the study.

The regeneration of injured tendons and ligaments is challenging because the scaffolds needs proper mechanical properties and a biomimetic morphology. In particular, the morphological arrangement of scaffolds is a key point to drive the cells growth to properly regenerate the collagen extracellular matrix. Electrospinning is a promising technique to produce hierarchically structured nanofibrous scaffolds able to guide cells in the regeneration of the injured tissue. Moreover, the dynamic stretching in bioreactors of electrospun scaffolds had demonstrated to speed up cell shape modifications in vitro. The aim of the present study was to combine different imaging techniques such as high-resolution X-ray tomography (XCT), scanning electron microscopy (SEM), fluorescence microscopy and histology to investigate if hierarchically structured poly (L-lactic acid) and collagen electrospun scaffolds can induce morphological modifications in human fibroblasts, while cultured in static and dynamic conditions. After 7 days of parallel cultures, the results assessed that fibroblasts had proliferated on the external nanofibrous sheath of the static scaffolds, elongating themselves circumferentially. The dynamic cultures revealed a preferential axial orientation of fibroblasts growth on the external sheath. The aligned nanofibre bundles inside the hierarchical scaffolds instead, allowed a physiological distribution of the fibroblasts along the nanofibre direction. Inside the dynamic scaffolds, cells appeared thinner compared with the static counterpart. This study had demonstrated that hierarchically structured electrospun scaffolds can induce different fibroblasts morphological modifications during static and dynamic conditions, modifying their shape in the direction of the applied loads. LAY DESCRIPTION: To enhance the regeneration of injured tendons and ligaments cells need to growth on dedicated structures (scaffolds) with mechanical properties and a fibrous morphology similar to the natural tissue. In particular, the morphological organisation of scaffolds is fundamental in leading cells to colonise them, regenerating the collagen extracellular matrix. Electrospinning is a promising technique to produce fibres with a similar to the human collagen fibres, suitable to design complex scaffolds able to guide cells in the reconstruction of the natural tissue. Moreover, it is well established that the cyclic stretching of these scaffolds inside dedicated systems called bioreactors, can speed up cells growth and their shape modification. The aim of the present study was to investigate how hierarchically structured electrospun scaffolds, made of resorbable material such as poly(L-lactic acid) and collagen, could induce morphological changes in human fibroblasts, while cultured during static and dynamic conditions. These scaffolds were composed by an external electrospun membrane that grouped inside it a ring-shaped bundle, made of axially aligned nanofibres, resembling the morphological arrangement of tendon and ligament tissue. After 7 days of parallel cultures, the scaffolds were investigated using the following imaging techniques: (i) high-resolution X-ray tomography (XCT); (ii) scanning electron microscopy (SEM); (iii) fluorescence microscopy and (iv) histology. The results showed that fibroblasts were able to grow on the external nanofibrous sheath of the static scaffolds, by elongating themselves along their circumference. The dynamic cultures revealed instead a preferential axial orientation of fibroblasts grown on the external sheath. The aligned nanofibre bundles inside the hierarchical scaffolds allowed an axial distribution of the fibroblasts along the nanofibres direction. This study has demonstrated that the electrospun hierarchically structured scaffolds investigated can modify the fibroblasts morphology both in static and dynamic conditions, in relation with the direction of the applied loads.

The outbreak of SARS-CoV-2 pandemic highlighted the worldwide lack of surgical masks and personal protective equipment, which represent the main defense available against respiratory diseases as COVID-19. At the time, masks shortage was dramatic in Italy, the first European country seriously hit by the pandemic: aiming to address the emergency and to support the Italian industrial reconversion to the production of surgical masks, a multidisciplinary team of the University of Bologna organized a laboratory to test surgical masks according to European regulations. The group, driven by the expertise of chemical engineers, microbiologists, and occupational physicians, set-up the test lines to perform all the functional tests required. The laboratory started its activity on late March 2020, and as of the end of December of the same year 435 surgical mask prototypes were tested, with only 42 masks compliant to the European standard. From the analysis of the materials used, as well as of the production methods, it was found that a compliant surgical mask is most likely composed of three layers, a central meltblown filtration layer and two external spunbond comfort layers. An increase in the material thickness (grammage), or in the number of layers, does not improve the filtration efficiency, but leads to poor breathability, indicating that filtration depends not only on pure size exclusion, but other mechanisms are taking place (driven by electrostatic charge). The study critically reviewed the European standard procedures, identifying the weak aspects; among the others, the control of aerosol droplet size during the bacterial filtration test results to be crucial, since it can change the classification of a mask when its performance lies near to the limiting values of 95 or 98%.

Vascular and traumatic injuries of the central nervous system are recognized as global health priorities. A polypharmacology approach that is able to simultaneously target several injury factors by the combination of agents having synergistic effects appears to be promising. Herein, we designed a polymeric delivery system loaded with two drugs, ibuprofen (Ibu) and thyroid hormone triiodothyronine (T3) to in vitro release the suitable amount of the anti-inflammation and the remyelination drug. As a production method, electrospinning technology was used. First, Ibu-loaded micro (diameter circa 0.95–1.20 µm) and nano (diameter circa 0.70 µm) fibers were produced using poly(l-lactide) PLLA and PLGA with different lactide/glycolide ratios (50:50, 75:25, and 85:15) to select the most suitable polymer and fiber diameter. Based on the in vitro release results and in-house knowledge, PLLA nanofibers (mean diameter = 580 ± 120 nm) loaded with both Ibu and T3 were then successfully produced by a co-axial electrospinning technique. The in vitro release studies demonstrated that the final Ibu/T3 PLLA system extended the release of both drugs for 14 days, providing the target sustained release. Finally, studies in cell cultures (RAW macrophages and neural stem cell-derived oligodendrocyte precursor cells—OPCs) demonstrated the anti-inflammatory and promyelinating efficacy of the dual drug-loaded delivery platform.

Reconstructions of ruptured tendons and ligaments currently have dissatisfactory failure rate. Failures are mainly due to the mechanical mismatch of commercial implants with respect to the host tissue. In fact, it is crucial to replicate the morphology (hierarchical in nature) and mechanical response (highly-nonlinear) of natural tendons and ligaments. The aim of this study was to develop morphologically bioinspired hierarchical Nylon 6,6 electrospun assemblies recreating the structure and performance of tendons and ligaments. First, we built different electrospun bundles to find the optimal orientation of the nanofibers. A 2nd-level hierarchical assembly was fabricated with a dedicated process that allowed tightly joining the bundles one next to the other with an electrospun sheath, so as to improve the mechanical performance. Finally, a further hierarchical 3rd-level assembly was constructed by grouping several 2nd-level assemblies. The morphology of the different structures was assessed with scanning electron microscopy and high-resolution X-ray tomography, which allowed measuring the directionality of the nanofibers in the bundles and in the sheaths. The mechanical properties of the single bundles and of the 2nd-level assemblies were measured with tensile tests. The single bundles and the hierarchical assemblies showed morphology and directionality of the nanofibers similar to the tendons and ligaments. The strength and stiffness were comparable to that of tendons and ligaments. In conclusion, this work showed an innovative electrospinning production process to build nanofibrous Nylon 6,6 hierarchical assemblies which are suitable as future implantable devices and able to mimic the multiscale morphology and the biomechanical properties of tendons and ligaments.

The selective removal of thin varnish layers from oil and egg tempera paintings is still an open challenge in the conservation field. In this paper, a new cleaning system was developed by using a gel composed of fully green components as deep eutectic solvents (DES) and agar. The gel, prepared admixing choline chloride -urea with an EtOH-H2O agar gel, exhibited good rheological properties in terms of gel stiffness, allowing easy handling and removal of the gel. The new developed cleaning gel was successfully tested for the removal of proteinaceous layers applied over both hydrophobic (linseed oil as binder) and hydrophilic (egg temperas as binder) surfaces. The procedure consists on two steps: first the choline chloride -urea agar gel was applied and let to act then an EtOH-H2O agar gel was applied for few seconds to allow the removal of the DES residues Moreover, an innovative non-destructive approach based on micro-Spatially Offset Raman Spectroscopy (micro-SORS) allowed to demonstrate how the gel impairs the diffusion of the cleaning agents in the paint layers, highlighting the good solvent retention ability of the gel.

An anomalous polystyrene gel was obtained during the copper-catalyzed “activators regenerated by electron transfer” “atom transfer radical polymerization” (ARGET ATRP) of styrene at 60–70 °C, using ascorbic acid/Na2CO3 as the reducing system and EtOAc/EtOH as the solvent mixture. The result is remarkable since no branching nor cross-linking reagents were added to the reaction mixture and their formation in situ was excluded. The anomalous PS branching, at the origin of the phenomenon, requires a generic bifunctional initiator and is mechanistically bound to termination reactions between bifunctional macroinitiators. As a matter of fact, the branching/cross-linking phenomenon loses intensity, or even disappears, under reaction conditions that cause the built-up of CuII or increase the chain polymerization rate. The temperature is also a critical variable since no branching was observed for temperatures higher than 90 °C. We believe that the route toward gelation starts with a controlled chain polymerization of styrene from the bifunctional initiator, soon integrated by a step-growth polymerization due to radical coupling of the terminal units. The progressive decrease in the number of chains and free radicals in the reaction mixture should make more and more probable the intramolecular coupling between the C−Cl ends of the remaining long and entangled chains, producing a polycatenane network. [Figure not available: see fulltext.]

New bio-based polymers capable of either outperforming fossil-based alternatives or possessing new properties and functionalities are of relevant interest in the framework of the circular economy. In this work, a novel bio-based polycarvone acrylate di-epoxide (PCADE) was used as an additive in a one-step straightforward electrospinning process to endow the fibres with functionalisable epoxy groups at their surface. To demonstrate the feasibility of the approach, poly(vinylidene fluoride) (PVDF) fibres loaded with different amounts of PCADE were prepared. A thorough characterisation by TGA, DSC, DMTA and XPS showed that the two polymers are immiscible and that PCADE preferentially segregates at the fibre surface, thus developing a very simple one-step approach to the preparation of ready-to-use surface functionalisable fibres. We demonstrated this by exploiting the epoxy groups at the PVDF fibre surface in two very different applications, namely in epoxy-based carbon fibre reinforced composites and membranes for ω-transaminase enzyme immobilisation for heterogeneous catalysis.