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In this work, assessment of microplastics (MPs) in commercial vegetable edible oils from Italy and Spain, including extra-virgin olive oil, olive oil, sunflower oil, and mixed seed oil, has been conducted for the first time. The method was based on sample dilution with ethanol:n-hexane (1:3, v/v), homogenization, vacuum filtration on macroporous silicon filters with 5 μm pore diameter to collect MPs, and automatic µ-FTIR spectroscopy for MPs detection and characterization. In the analysis of oil samples, a mean MPs abundance of 1140 ± 350 MPs/L was found. Observed MPs were characterized, being most of them fragments (81.2 %), with particle sizes < 100 µm (77.5 %), and mainly composed of polyethylene (50.3 %) and polypropylene (28.7 %), among others. Statistical analysis revealed that there were not significant differences (p-value > 0.05) in the abundance of MPs between oil samples or types., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Multiple sclerosis (MS) is a chronic autoimmune disorder that affects the central nervous system and can result in various symptoms, including muscle weakness, spasticity, and fatigue, ultimately leading to the deterioration of the musculoskeletal system. However, in recent years, exosuits have emerged as a game-changing solution to assist individuals with MS during their daily activities. These lightweight and affordable wearable robotic devices have gained immense popularity. In our study, we assessed the performance of an elbow exosuit on eight individuals with MS using high-density electromyography to measure biceps muscle activity. The results demonstrated that our prototype significantly reduced muscle effort during both dynamic and isometric tasks while increasing the elbow range of motion. In addition, the exosuit effectively delayed the onset of muscle fatigue, enhancing endurance for people with MS and enabling them to perform heavy duty tasks for a longer period.

Cardiovascular disease (CVD), the leading cause of death globally, affects the heart and arteries with a variety of clinical manifestations, the most dramatic of which are myocardial infarction (MI), abdominal aortic aneurysm (AAA), and intracranial aneurysm (IA) rupture. In MI, necrosis of the myocardium, scar formation, and loss of cardiomyocytes result from insufficient blood supply due to coronary artery occlusion. Beyond stenosis, the arteries that are structurally and functionally connected to the cardiac tissue can undergo pathological dilation, i.e., aneurysmal dilation, with high risk of rupture. Aneurysms of the intracranial arteries (IAs) are more commonly seen in young adults, whereas those of the abdominal aorta (AAA) are predominantly seen in the elderly. IAs, unpredictably, can undergo rupture and cause life-threatening hemorrhage, while AAAs can result in rupture, internal bleeding and high mortality rate. In this clinical context, hydrogels, three-dimensional networks of water-seizing polymers, have emerged as promising biomaterials for cardiovascular tissue repair or protection due to their biocompatibility, tunable properties, and ability to encapsulate and release bioactive molecules. This review provides an overview of the current state of research on the use of hydrogels as an innovative platform to promote cardiovascular-specific tissue repair in MI and functional recovery or protection in aneurysmal dilation.

Cardiac tissue engineering is a cutting-edge technology aiming to replace irreversibly damaged cardiac tissue and restore contractile functionality. However, cardiac tissue engineering porous and perfusable scaffolds to enable oxygen supply in vitro and eventually promote angiogenesis in vivo are still desirable. Two fully-aliphatic random copolymers of poly(butylene succinate) (PBS), poly(butylene succinate/Pripol), P(BSBPripol), and poly(butylene/neopentyl glycol succinate), P(BSNS), containing two different subunits, neopentyl glycol and Pripol 1009, were successfully synthesized and then electrospun in tridimentional fibrous mats. The copolymers show different thermal and mechanical behaviours as result of their chemical structure. In particular, copolymerization led to a reduction in crystallinity and consequently PBS stiffness, reaching values of elastic modulus very close to those of soft tissues. Then, to check the biological suitability, human induced Pluripotent Stem Cells (hiPSCs) were directly seeded on both PBS-based copolymeric scaffolds. The results confirmed the ability of both the scaffolds to sustain cell viability and to maintain their stemness during cell expansion. Furthermore, gene expression and immunofluorescence analysis showed that P(BSBPripol) scaffold promoted an upregulation of the early cardiac progenitor and later-stage markers with a simultaneously upregulation of HYPPO pathway gene expression, crucial for mechanosensing of cardiac progenitor cells. These results suggest that the correct ad-hoc chemical design and, in turn, the mechanical properties of the matrix, such as substrate stiffness, together with surface porosity, play a critical role in regulating the behaviour of cardiac progenitors, which ultimately offers valuable insights into the development of novel bio-inspired scaffolds for cardiac tissue regeneration., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

The use of portable and lightweight wearable assistive devices can improve wearer locomotion efficiency by reducing the metabolic cost of walking. To achieve this goal, assistive technologies must adapt to different locomotion modes to optimize walking assistance. In this work, we developed a novel control strategy for an underactuated soft exosuit featuring a single actuator to assist bilateral hip flexion, which utilized inertial measurement units (IMUs) to discriminate between three different locomotion modes: walking up/down stairs or on level ground. Walking assistance was adjusted in real-time to maximize the assistance provided to the user. In order to preliminary test the effectiveness of this control strategy, four healthy subjects performed a walking task with the exosuit disabled (Exo Off) and enabled (Exo On). Results showed that the kinematics-based IMU classification strategy achieved an overall accuracy exceeding 95% across the three-movement patterns. Subjects were able to save an average of 10.1% on walking energy expenditure with assistance from the wearable device. This work contributes to the development of compact, high-performance lower limb assistive technologies and their development in practical applications.

Here, we present novel biocompatible poly(butylene trans -1,4-cyclohexanedicarboxylate) (PBCE)-based random copolymer nanostructured scaffolds with tailored stiffness and hydrophilicity. The introduction of a butylene diglycolate (BDG) co-unit, containing ether oxygen atoms, along the PBCE chain remarkably improved the hydrophilicity and chain flexibility. The copolymer containing 50 mol% BDG co-units (BDG50) and the parent homopolymer (PBCE) were synthesized and processed as electrospun scaffolds and compression-molded films, added for the sake of comparison. We performed thermal, wettability, and stress-strain measures on the PBCE-derived scaffolds and films. We also conducted biocompatibility studies by evaluating the adhesion and proliferation of multipotent mesenchymal/stromal cells (hBM-MSCs) on each polymeric film and scaffold. We demonstrated that solid-state properties can be tailored by altering sample morphology besides chemical structure. Thus, scaffolds were characterized by a higher hydrophobicity and a lower elastic modulus than the corresponding films. The three-dimensional nanostructure conferred a higher adsorption protein capability to the scaffolds compared to their film counterparts. Finally, the PBCE and BDG50 scaffolds were suitable for the long-term culture of hBM-MSCs. Collectively, the PBCE homopolymer and copolymer are good candidates for tissue engineering applications.

Mechanotransduction is a molecular process by which cells translate physical stimuli exerted by the external environment into biochemical pathways to orchestrate the cellular shape and function. Even with the advancements in the field, the molecular events leading to the signal cascade are still unclear. The current biotechnology of tissue engineering offers the opportunity to study in vitro the effect of the physical stimuli exerted by biomaterial on stem cells and the mechanotransduction pathway involved in the process. Here, we cultured multipotent human mesenchymal/stromal cells (hMSCs) isolated from bone marrow (hBM-MSCs) and adipose tissue (hASCs) on films of poly(butylene 1,4-cyclohexane dicarboxylate) (PBCE) and a PBCE-based copolymer containing 50 mol% of butylene diglycolate co-units (BDG50), to intentionally tune the surface hydrophilicity and the stiffness (PBCE = 560 Mpa; BDG50 = 94 MPa). We demonstrated the activated distinctive mechanotransduction pathways, resulting in the acquisition of an elongated shape in hBM-MSCs on the BDG50 film and in maintaining the canonical morphology on the PBCE film. Notably, hASCs acquired a new, elongated morphology on both the PBCE and BDG50 films. We found that these events were mainly due to the differences in the expression of Cofilin1, Vimentin, Filamin A, and Talin, which established highly sensitive machinery by which, rather than hASCs, hBM-MSCs distinguished PBCE from BDG50 films.

Among novel renewable furanoate-based polyesters, poly(pentamethylene 2,5-furandicarboxylate) (PPeF) shows outstanding gas barrier properties and high flexibility. PPeF blending/copolymerization with another well-known bio-based polymer, poly(lactic acid) (PLA), leads to considerably better mechanical and gas barrier properties of the latter, making it suitable for flexible food packaging applications. In this work, enzymatic depolymerization of PLA/PPeF blends with different compositions (1, 3, 5, 20, 30, and 50 wt % PPeF) and a PLA-PPeF block copolymer (50 wt % PPeF) by cutinase 1 from Thermobifida cellul ositilytica (Thc&#95;Cut1) was investigated as a possible recycling strategy. Based on quantification of weight loss and high-performance liquid chromatography (HPLC) analysis of released molecules, faster hydrolysis was seen for PLA/PPeF blends with increasing PPeF content when compared to neat PLA, while the block copolymer (P(LA50PeF50)) was significantly less susceptible to hydrolysis. Surface morphology analysis (via scanning electron microscopy), Fourier transform infrared spectroscopy, and NMR analysis confirmed preferential hydrolysis of the PPeF component. Through crystallization, 2,5-furandicarboxylic acid was selectively recovered from the depolymerized films and used for the resynthesis of the PPeF homopolymer, demonstrating the potential of enzymes for novel recycling concepts. The possibility of selective recovery of 2,5-furandicarboxylic acid from the completely depolymerized films with a 75% yield could bring further evidence of the high value of these materials, both in the form of blends and copolymers, for a sustainable whole packaging life cycle, where PPeF is potentially enzymatically recycled and PLA is mechanically recycled., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

High molecular weight, fully biobased random copolymers of 2,5-furandicarboxylic acid (2,5-FDCA) containing different amounts of (1R, 3S)-(+)-Camphoric Acid (CA) have been successfully synthesized by two-stage melt polycondensation and compression molding in the form of films. The synthesized copolyesters have been first subjected to molecular characterization by nuclear magnetic resonance spectroscopy and gel-permeation chromatography. Afterward, the samples have been characterized from a thermal and structural point of view by means of differential scanning calorimetry, thermogravimetric analysis, and wide-angle X-ray scattering, respectively. Mechanical and barrier properties to oxygen and carbon dioxide were also tested. The results obtained revealed that chemical modification permitted a modulation of the abovementioned properties depending on the amount of camphoric co-units present in the copolymers. The outstanding functional properties promoted by camphor moieties addition could be associated with improved interchain interactions (π-π ring stacking and hydrogen bonds).

In the last years, the exponential growth in the demand of petroleum-based plastic materials, besides the extreme exploitation of nonrenewable resources, lead to the mismanagement of their disposal and to serious ecological issues related to their dispersion in the environment. Among the possible practical solutions, the design of biobased and biodegradable polymers represents one of the most innovative challenges. In such a context, the eco-design of an aromatic-aliphatic multiblock copolymer based on poly(lactic acid) and containing 2,5-furandicarboxylic acid was carried out with the aim of improving the properties of poly(l-lactic acid) for sustainable packaging applications. The synthetic method followed a novel top-down approach, starting from industrial high-molecular-weight poly(l-lactic acid) (PLLA), which was reacted with 1,5-pentanediol to get hydroxyl-terminated PLLA and then chain-extended with hydroxyl-terminated poly(pentamethylene furanoate) (PPeF-OH). The final copolymer, called P(LLA50PeF50)-CE, was subjected to molecular, structural, and thermal characterization. Tensile and gas permeability tests were also carried out. According to the results obtained, PLLA thermal stability was improved, being the range of processing temperatures widened, and its stiffness and brittleness were decreased, making the new material suitable for the realization of films for flexible packaging. The oxygen permeability of PLLA was decreased by 40% and a similar improvement was measured also for carbon dioxide. P(LLA50PeF50)-CE was found to be completely biodegraded within 60 days of composting treatment. In terms of mechanism, the blocks of PPeF and PLLA were demonstrated to undergo surface erosion and bulk hydrolysis, respectively. In terms of kinetics, PPeF blocks degraded slower than PLLA ones.

Bimanual object manipulation involves using both hands to interact with objects in the environment, and the process requires the central nervous system to process sensory feedback and translate it into motor commands. Although there have been significant advancements in haptics and robotics, the kinematic strategies involved in bimanual coupled tasks are still not fully understood. This study aimed to investigate the dynamic interaction between hands during the manipulation of a shared object using two impedance-controlled exoskeletons programmed to simulate bimanual coupled manipulation of virtual objects. Twenty-six participants (right-handed and left-handed) were asked to use both hands to grab and place simulated objects in specific locations. The virtual objects were rendered with four different dynamic properties, affecting the manipulation strategies used to complete the tasks. The results showed that force asymmetries were related to movement direction and handedness preference, with right-handers exhibiting asymmetries related to movement direction and left-handers showing better control of the force applied between their hands. This is possibly due to their constant exposure to objects designed for right-handed use. Additionally, the haptic properties of the virtual objects influenced task performance in terms of timing and failure for all participants. This study demonstrates the potential of advanced technologies to provide realistic simulations of multi-joint movements involving the entire upper extremities. The findings have implications for the development of training programs for bimanual object manipulation tasks and the design of virtual environments that can enhance the learning process.

Estimation of the force exerted by muscles from their electromyographic (EMG) activity may be useful to control robotic devices. Approximating end-point forces as a linear combination of the activities of multiple muscles acting on a limb may lead to an inaccurate estimation because of the dependency between the EMG signals, i.e., multi-collinearity. This study compared the EMG-to-force mapping estimation performed with standard multiple linear regression and with three other algorithms designed to reduce different sources of the detrimental effects of multi-collinearity: Ridge Regression, which performs an L2 regularization through a penalty term; linear regression with constraints from foreknown anatomical boundaries, derived from a musculoskeletal model; linear regression of a reduced number of muscular degrees of freedom through the identification of muscle synergies. Two datasets, both collected during the exertion of submaximal isometric forces along multiple directions with the upper limb, were exploited. One included data collected across five sessions and the other during the simultaneous exertion of force and generation of different levels of co-contraction. The accuracy and consistency of the EMG-to-force mappings were assessed to determine the strengths and drawbacks of each algorithm. When applied to multiple sessions, Ridge Regression achieved higher accuracy (R 2 = 0.70) but estimations based on muscle synergies were more consistent (differences between the pulling vectors of mappings extracted from different sessions: 67%). In contrast, the implementation of anatomical constraints was the best solution, both in terms of consistency (R 2 = 0.64) and accuracy (74%), in the case of different co-contraction conditions. These results may be used for the selection of the mapping between EMG and force to be implemented in myoelectrically controlled robotic devices.

Fully bio-based poly(lactic acid) (PLA) and poly(3-hydroxybutyrate) (PHB) blends plasticized with tributyrin (TB), and their nanocomposite based on chitin nanoparticles (ChNPs) was developed using melt mixing followed by a compression molding process. The combination of PHB and ChNPs had an impact on the crystallinity of the plasticized PLA matrix, thus improving its oxygen and carbon dioxide barrier properties as well as displaying a UV light-blocking effect. The addition of 2 wt% of ChNP induced an improvement on the initial thermal degradation temperature and the overall migration behavior of blends, which had been compromised by the presence of TB. All processed materials were fully disintegrated under composting conditions, suggesting their potential application as fully biodegradable packaging materials.

Haptic feedback is the sensory modality to enhance the so-called "immersion", meant as the extent to which senses are engaged by the mediated environment during virtual reality applications. However, it can be challenging to meet this requirement using conventional robotic design approaches that rely on rigid mechanical systems with limited workspace and bandwidth. An alternative solution can be seen in the adoption of lightweight wearable systems equipped with Neuromuscular Electrical Stimulation (NMES): in fact, NMES offers a wide range of different forces and qualities of haptic feedback. In this study, we present an experimental setup able to enrich the virtual reality experience by employing NMES to create in the antagonists' muscles the haptic sensation of being loaded. We developed a subject-specific biomechanical model that estimated elbow torque during object lifting to deliver suitable electrical muscle stimulations. We experimentally tested our system by exploring the differences between the implemented NMES-based haptic feedback ( NMES condition), a physical lifted object ( Physical condition), and a condition without haptic feedback ( Visual condition) in terms of kinematic response, metabolic effort, and participants' perception of fatigue. Our results showed that both in terms of metabolic consumption and user fatigue perception, the condition with electrical stimulation and the condition with the real weight differed significantly from the condition without any load: the implemented feedback was able to faithfully reproduce interactions with objects, suggesting its possible application in different areas such as gaming, work risk assessment simulation, and education.

Neuromuscular functional electrical stimulation represents a valid technique for functional rehabilitation or, in the form of a neuroprosthesis, for the assistance of neurological patients. However, the selected stimulation of single muscles through surface electrodes remains challenging particularly for the upper extremity. In this paper, we present the MyoCeption, a comprehensive setup, which enables intuitive modeling of the user's musculoskeletal system, as well as proportional stimulation of the muscles with 16-bit resolution through up to 10 channels. The system can be used to provide open-loop force control, which, if coupled with an adequate body tracking system, can be used to implement an impedance control where the control loop is closed around the body posture. The system is completely self-contained and can be used in a wide array of scenarios, from rehabilitation to VR to teleoperation. Here, the MyoCeption's control environment has been experimentally validated through comparison with a third-party simulation suite. The results indicate that the musculoskeletal model used for the MyoCeption provides muscle geometries that are qualitatively similar to those computed in the baseline model.

Patients suffering from neuromuscular diseases experience motor disabilities which hinder their independence during activities of daily living (ADLs). For such impaired subjects, robotic devices and Functional Electrical Stimulation (FES) are technologies commonly used to rehabilitate lost functions. Nevertheless, both systems present some limitations, and merging FES and robots in Hybrid Robotic Rehabilitation Systems allows to overcome these boundaries. Here we propose for the first time a hybrid cooperative controller involving FES and a soft wearable upper arm exosuit to rehabilitate elbow movements. We tested the designed hybrid controller on six healthy participants. The results showed how the proposed hybrid controller allowed the wearers to perform flexion movements with no significant decrease in accuracy and precision with respect to the exosuit alone, while significantly decreasing the fatigue level by about 63% and delaying its onset with respect to the FES action alone.

Using a computer vision approach we have extracted the Haralick's texture features of randomly oriented electrospun nanomaterials in order to predict the proliferative behavior of cells which were subsequently seeded onto the nanosurfaces., Competing Interests: The authors declare that there are not conflicting interests., (This journal is © The Royal Society of Chemistry.)

In the past 20 years, scientific research focused on the identification of valid alternatives to materials of fossil origin, in particular, related to biobased polymers. Recently, the efforts led to the synthesis of thiophene-based polymers (TBPs), a new class of polyesters based on 2,5-thiophenedicarboxylic acid (TPCA) that can be industrially produced using biomass-derived molecules. In this study, TBPs were synthesized using diols with different chain length (from C4 to C6) leading to poly(butylene 2,5-thiophenedicarboxylate) (PBTF), poly(pentamethylene 2,5-thiophenedicarboxylate) (PPeTF), and poly(hexamethylene 2,5-thiophenedicarboxylate) (PHTF), respectively, that were processed to thin films. To investigate enzymatic hydrolysis of these polymer films, cutinase 1 (Thc&#95;cut1) and cutinase 2 (Thc&#95;cut2) from Thermobifida cellulosilytica were recombinantly expressed in the host E. coli and purified. After 72 h of incubation at 65°C with 5 µM Thc&#95;cut1, weight loss and HPLC analysis indicated 9, 100, and 80% degradation of PBTF, PPeTF, and PHTG with a concomitant release of 0.12, 2.70, and 0.67 mM of TPCA. The SEM analysis showed that tiny holes were formed on the surface of the films and after 72 h PPeTF was completely degraded. The LC-TOF/MS analysis indicated that Thc&#95;cut2 in particular released various oligomers from the polymer during the reaction. In addition, the FTIR analysis showed the formation of novel acid and hydroxyl groups on the polymer surfaces. The results showed that the two used thermostable cutinases are promising biocatalysts for the environmentally friendly degradation of TPCA-based polyesters, in view of a possible sustainable recycling of plastic waste through resynthesis processes., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Bertolini, Soccio, Weinberger, Guidotti, Gazzano, Guebitz, Lotti and Pellis.)

The growing field of soft wearable exosuits, is gradually gaining terrain and proposing new complementary solutions in assistive technology, with several advantages in terms of portability, kinematic transparency, ergonomics, and metabolic efficiency. Those are palatable benefits that can be exploited in several applications, ranging from strength and resistance augmentation in industrial scenarios, to assistance or rehabilitation for people with motor impairments. To be effective, however, an exosuit needs to synergistically work with the human and matching specific requirements in terms of both movements kinematics and dynamics: an accurate and timely intention-detection strategy is the paramount aspect which assume a fundamental importance for acceptance and usability of such technology. We previously proposed to tackle this challenge by means of a model-based myoelectric controller, treating the exosuit as an external muscular layer in parallel to the human biomechanics and as such, controlled by the same efferent motor commands of biological muscles. However, previous studies that used classical control methods, demonstrated that the level of device's intervention and effectiveness of task completion are not linearly related: therefore, using a newly implemented EMG-driven controller, we isolated and characterized the relationship between assistance magnitude and muscular benefits, with the goal to find a range of assistance which could make the controller versatile for both dynamic and static tasks. Ten healthy participants performed the experiment resembling functional daily activities living in separate assistance conditions: without the device's active support and with different levels of intervention by the exosuit. Higher assistance levels resulted in larger reductions in the activity of the muscles augmented by the suit actuation and a good performance in motion accuracy, despite involving a decrease of the movement velocities, with respect to the no assistance condition. Moreover, increasing torque magnitude by the exosuit resulted in a significant reduction in the biological torque at the elbow joint and in a progressive effective delay in the onset of muscular fatigue. Thus, contrarily to classical force and proportional myoelectric schemes, the implementation of an opportunely tailored EMG-driven model based controller affords to naturally match user's intention detection and provide an assistance level working symbiotically with the human biomechanics., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2020 Missiroli, Lotti, Xiloyannis, Sloot, Riener and Masia.)

Herein, we present poly(butylene 1,4-cyclohexanedicarboxylate) (PBCE) films characterized by an unpatterned microstructure and a specific hydrophobicity, capable of boosting a drastic cytoskeleton architecture remodeling, culminating with the neuronal-like differentiation of human bone marrow-mesenchymal stem cells (hBM-MSCs). We have used two different filming procedures to prepare the films, solvent casting (PBCE) and compression-moulding (PBCE*). PBCE film had a rough and porous surface with spherulite-like aggregations (Ø = 10-20 μm) and was characterized by a water contact angle = 100°. PBCE* showed a smooth and continuous surface without voids and visible spherulite-like aggregations and was more hydrophobic (WCA = 110°). Both surface characteristics were modulated through the copolymerization of different amounts of ether-oxygen-containing co-units into PBCE chemical structure. We showed that only the surface characteristics of PBCE-solvent-casted films steered hBM-MSCs toward a neuronal-like differentiation. hBM-MSCs lost their canonical mesenchymal morphology, acquired a neuronal polarized shape with a long cell protrusion (≥150 μm), expressed neuron-specific class III β-tubulin and microtubule-associated protein 2 neuronal markers, while nestin, a marker of uncommitted stem cells, was drastically silenced. These events were observed as early as 2-days after cell seeding. Of note, the phenomenon was totally absent on PBCE* film, as hBM-MSCs maintained the mesenchymal shape and behavior and did not express neuronal/glial markers.

Fully biobased blends of thermoplastic starch and a poly(butylene cyclohexanedicarboxylate)-based random copolyester containing 25 % of adipic acid co-units (PBCEA) are prepared by melt blending and direct extrusion film casting. The obtained films are characterized from the physicochemical and mechanical point of view and their fragmentation under composting conditions is evaluated. The results demonstrate that the introduction of adipic acid co-units in the PBCE macromolecular chains permits to decrease the blending temperature, thus avoiding unwanted starch degradation reactions. Moreover, the presence of small amounts of citric acid as compatibilizer further improves the interfacial adhesion between the two components and promotes the formation of micro-porosities within the films. The synergistic combination of these factors leads to the development of materials showing an elastomeric behavior, i.e. no evident yield and elongation at break higher than 450 %, good moisture resistance and fast fragmentation in compost., Competing Interests: Declaration of Competing Interest The authors declare no conflict of interest., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

In the present paper, four fully biobased homopolyesters of 2,5-furandicarboxylic acid (2,5-FDCA) with a high molecular weight have been successfully synthesized by two-stage melt polycondensation, starting from the dimethyl ester of 2,5-FDCA and glycols of different lengths (the number of methylene groups ranged from 3 to 6). The synthesized polyesters have been first subjected to an accurate molecular characterization by NMR and gel-permeation chromatography. Afterward, the samples have been successfully processed into free-standing thin films (thickness comprised between 150 to 180 μm) by compression molding. Such films have been characterized from the structural (by wide-angle X-ray scattering and small-angle X-ray scattering), thermal (by differential scanning calorimetry and thermogravimetric analysis), mechanical (by tensile test), and gas barrier (by permeability measurements) point of view. The glycol subunit length was revealed to be the key parameter in determining the kind and fraction of ordered phases developed by the sample during compression molding and subsequent cooling. After storage at room temperature for one month, only the homopolymers containing the glycol subunit with an even number of -CH 2 - groups (poly(butylene 2,5-furanoate) (PBF) and poly(hexamethylene 2,5-furanoate) (PHF)) were able to develop a three-dimensional ordered crystalline phase in addition to the amorphous one, the other two appearing completely amorphous (poly(propylene 2,5-furanoate (PPF) and poly(pentamethylene 2,5-furanoate) (PPeF)). From X-ray scattering experiments using synchrotron radiation, it was possible to evidence a third phase characterized by a lower degree of order (one- or two-dimensional), called a mesophase, in all the samples under study, its fraction being strictly related to the glycol subunit length: PPeF was found to be the sample with the highest fraction of mesophase followed by PHF. Such a mesophase, together with the amorphous and the eventually present crystalline phase, significantly impacted the mechanical and barrier properties, these last being particularly outstanding for PPeF, the polyester with the highest fraction of mesophase among those synthesized in the present work., Competing Interests: The authors declare no competing financial interest.

Poly(2,5-alkylene furanoate)s are bio-based, smart, and innovative polymers that are considered the most promising materials to replace oil-based plastics. These polymers can be synthesized using ecofriendly approaches, starting from renewable sources, and result into final products with properties comparable and even better than those presented by their terephthalic counterparts. In this work, we present the molecular dynamics of four 100% bio-based poly(alkylene 2,5-furanoate)s, using broadband dielectric spectroscopy measurements that covered a wide temperature and frequency range. We unveiled complex local relaxations, characterized by the simultaneous presence of two components, which were dependent on thermal treatment. The segmental relaxation showed relaxation times and strengths depending on the glycolic subunit length, which were furthermore confirmed by high-frequency experiments in the molten region of the polymers. Our results allowed determining structure-property relations that are able to provide further understanding about the excellent barrier properties of poly(alkylene 2,5-furanoate)s. In addition, we provide results of high industrial interest during polymer processing for possible industrial applications of poly(alkylene furanoate)s.

Plastics remarkably contribute to marine litter, which is raising serious concerns. Currently, little is known about the fate of most plastics entering the marine environment and their potential biodegradation rate and extent under anoxic conditions. In this work, biodegradation of polyvinyl chloride (PVC) films by consortia enriched from marine samples (litter and water) was evaluated in anaerobic microcosms. After 7 months, three microcosms showed dense biofilms on plastic surfaces, gravimetric weight losses up to 11.7 ± 0.6%, marked decreases in thermal stability and average molecular weight of the polymer, suggesting microbial attack towards polymer chains. After 24 months, further three consortia showed the same abilities. Microbial communities analyzed at month 24 included taxa closely related to those previously reported as halogenated organic compounds degraders. The study is the first report on PVC biodegradation by marine anaerobic microbes and provides insights on potential biodegradation of the plastic film introduced into the sea by native microbes., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Tammann's two-stage crystal-nuclei-development method is applied for analysis of the thermal stability of homogenously formed crystal nuclei of poly(butylene isophthalate) (PBI) as well as their possible reorganization on transferring them to the growth temperature, using fast scanning chip calorimetry. Crystal nuclei were formed at 50 °C, that is, at a temperature only slightly higher than the glass transition temperature, and developed to crystals within a pre-defined time at the growth temperature of 85 °C. The number of nuclei, overcritical at the growth temperature, was detected as a function of the transfer-conditions (maximum temperature, heating rate) by evaluation of the developed crystal fraction. For different size-distributions of crystal nuclei, as controlled by the nucleation time, there is detected distinct reduction of the nuclei number on heating to maximum temperatures higher than about 90 to 110 °C, with the latter value holding for longer nucleation time. Longer nucleation allows for both increasing the absolute nuclei number and generation of an increased fraction of larger nuclei. Heating at 1000 K/s to 140-150 °C causes "melting" of even the most stable nuclei. While direct transfer of crystal nuclei from the nucleation temperature (50 °C) to the growth temperature (85 °C) reveals negligible effect of the transfer-heating rate, in-between heating to higher temperatures is connected with distinct nuclei-reorganization above 85 °C on heating slower than 1000-10.000 K/s. The performed study not only provides specific valuable information about the thermal characteristics of crystal nuclei of PBI but also highlights the importance of proper design of Tammann's nuclei development experiment for analysis of nuclei numbers. With the evaluation of critical rates of temperature-change for suppression of non-isothermal formation of both nuclei and crystals, the kinetics of crystallization of the slow crystallizing PBI is further quantified.

Dye-sensitized photooxygenation reaction of bio-based double bond-containing substrates is proposed as sustainable functionalization of terpenes and terpenoids to transform them into polyoxygenated compounds to be employed for the synthesis of new bio-based polyesters. As proof of concept, citronellol 1 has been regioselectively converted into diol 4 using singlet oxygen ( 1 O 2 ), a traceless reagent that can be generated from air, visible light and zeolite supported-photosensitizer (Thionine-NaY). With our synthetic approach, diol 4 has been obtained in two-steps, with good regioselectivity, using green reagents such as light and air, and finally a solvent-free oxidation step. From this compound, a citronellol-based copolyester of poly(butylene succinate) (PBS) has been synthesized and fully characterized. The results obtained evidence that the proposed copolymerization of PBS with the citronellol-based building blocks allows to obtain a more flexible and functionalizable material, by exploiting a largely available natural molecule modified through a green synthetic path., (Copyright © 2020 Lanteri, Quattrosoldi, Soccio, Basso, Cavallo, Munari, Riva, Lotti and Moni.)

The crystallization behavior of fully biobased poly(butylene isophthalate) (PBI) has been investigated using calorimetric and microscopic techniques. PBI is an extremely slow crystallizing polymer that leads, after melt-crystallization, to the formation of lamellar crystals and rather large spherulites, due to the low nuclei density. Based upon quantitative analysis of the crystal-nucleation behavior at low temperatures near the glass transition, using Tammann's two-stage nuclei development method, a nucleation pathway for an acceleration of the crystallization process and for tailoring the semicrystalline morphology is provided. Low-temperature annealing close to the glass transition temperature ( T g ) leads to the formation of crystal nuclei, which grow to crystals at higher temperatures, and yield a much finer spherulitic superstructure, as obtained after direct melt-crystallization. Similarly to other slowly crystallizing polymers like poly(ethylene terephthalate) or poly(l-lactic acid), low-temperature crystal-nuclei formation at a timescale of hours/days is still too slow to allow non-spherulitic crystallization. The interplay between glass relaxation and crystal nucleation at temperatures slightly below T g is discussed.

Plastics are perceived as modern and versatile materials, but their use is linked to numerous environmental issues as their production is based on finite raw materials (petroleum or natural gas). Additionally, their low biodegradability results in the accumulation of microplastics. As a result, there is extensive interest in the production of new, environmentally friendly, bio-based and biodegradable polymers. In this context, poly(ethylene vanillate) (PEV) has a great potential as a potentially bio-based alternative to poly(ethylene terephthalate); however, it has not yet been extensively studied. In the present work, the preparation of PEV is reported. The enthalpy and the entropy of fusion of the pure crystalline PEV have been estimated for the first time. Additionally, the equilibrium melting temperature has also been calculated. Furthermore, the isothermal and non-isothermal crystallization behavior are reported in detail, and new insights on the thermal stability and degradation mechanism of PEV are given.

The accumulation of high amounts of petroleum-derived plastics in the environment has raised ecological and health concerns. The aim of this work was to study the biodegradative abilities of five bacterial strains, namely Pseudomonas chlororaphis, Pseudomonas citronellolis, Bacillus subtilis, Bacillus flexus and Chelatococcus daeguensis, towards polyethylene, polypropylene, polystyrene and polyvinyl chloride films under aerobic conditions. Preliminary screening resulted in the selection of P. citronellolis and B. flexus as potential PVC film degraders. Both strains were able to form a biofilm on the plastic film surface and to cause some modifications to the FTIR spectra of biomass-free PVC films. The two strains were then used to set up a PVC film biodegradation assay in 2-liter flasks. After 45 days incubation, fragmentation of the film was observed, suggesting that PVC biodegradative activity took place. Gel permeation chromatography analysis showed a reduction in average molecular weight of 10% for PVC incubated with P. citronellolis, with PVC polymer chains apparently attacked. Based on these results, the P. citronellolis strain was selected for biodegradation assays of two waste PVC films, used either nonsterile or subjected to ethanol sterilization. Chemical analyses on the incubated films confirmed the biodegradation of waste PVC plastics as shown by a gravimetric weight loss of up to about 19% after 30 days incubation. In summary, this work reports the biodegradation of PVC films by P. citronellolis and B. flexus. Both strains were shown to act mainly against PVC additives, exhibiting a low biodegradation rate of PVC polymer., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Edible films and coatings gained renewed interest in the food packaging sector with polysaccharide and protein blending being explored as a promising strategy to improve properties of edible films. The present work studies composite edible films in different proportions of pectin (P), alginate (A) and whey Protein concentrate (WP) formulated with a simplex centroid mixture design and evaluated for physico-chemical characteristics to understand the effects of individual components on the final film performance. The studied matrices exhibited good film forming capacity, except for whey protein at a certain concentration, with thickness, elastic and optical properties correlated to the initial solution viscosity. A whey protein component in general lowered the viscosity of the initial solutions compared to that of alginate or pectin solutions. Subsequently, a whey protein component lowered the mechanical strength, as well as the affinity for water, as evidenced from an increasing contact angle. The effect of pectin was reflected in the yellowness index, whereas alginate and whey protein affected the opacity of film. Whey protein favored higher opacity, lower gas barrier values and dense structures, resulting from the polysaccharide-protein aggregates. All films displayed however good thermal stability, with degradation onset temperatures higher than 170 °C.

In this paper, we present a prototype of an innovative portable shoulder exoskeleton for human assistance and augmentation. The device provides torques to flexion/extension movements of the shoulder, compensating for gravitational forces, and is passively compliant along the remaining degrees of freedom letting the shoulder moving along them. The novelty of our system is a flexible link, made of a hyper-redundant passive structure, that avoids joint misalignment by adapting to the complex movements of the humerus head, similarly to a soft component. The flexible link is compliant to rotations around one axis but rigid around the other two axes, allowing transmission of flexion/extension torque but kinematically transparent along the remaining degrees of freedom. The device is light weight and allows to cover around the 82% of the shoulder flexion/extension range of motion. The exoskeleton was tested on a cohort of 5 healthy subjects, monitoring shoulder kinematics, interaction forces and acquiring the electromyography of three major muscles contributing to shoulder flexion. During both static postures and dynamic movements, assistance from the exoskeleton resulted in a significant reduction of muscular effort in the anterior (-32.2% in static, -25.3% in dynamic) and medial deltoid (56.9% in static, -49.6% in dynamic) and an average reduction of the biceps brachii.

We report the study of novel biodegradable electrospun scaffolds from poly(butylene 1,4-cyclohexandicarboxylate- co -triethylene cyclohexanedicarboxylate) (P(BCE- co -TECE)) as support for in vitro and in vivo muscle tissue regeneration. We demonstrate that chemical composition, i.e., the amount of TECE co-units (constituted of polyethylene glycol-like moieties), and fibre morphology, i.e., aligned microfibrous or sub-microfibrous scaffolds, are crucial in determining the material biocompatibility. Indeed, the presence of ether linkages influences surface wettability, mechanical properties, hydrolytic degradation rate, and density of cell anchoring points of the studied materials. On the other hand, electrospun scaffolds improve cell adhesion, proliferation, and differentiation by favouring cell alignment along fibre direction (fibre morphology), also allowing for better cell infiltration and oxygen and nutrient diffusion (fibre size). Overall, C2C12 myogenic cells highly differentiated into mature myotubes when cultured on microfibres realised with the copolymer richest in TECE co-units (micro-P73 mat). Lastly, when transplanted in the tibialis anterior muscles of healthy, injured, or dystrophic mice, micro-P73 mat appeared highly vascularised, colonised by murine cells and perfectly integrated with host muscles, thus confirming the suitability of P(BCE- co -TECE) scaffolds as substrates for skeletal muscle tissue engineering.

Thermal, structural and physico-chemical properties of different composite edible films based on alginate and pectin with the addition of citral essential oil (citral EO) as an agent to improve barrier properties, were investigated. The obtained films were clear and transparent, with a yellow hue that increased with citral EO addition. All the films displayed good thermal stability up to 160 °C, with a slight improvement observed by increasing the amount of citral EO in the composites. Gas transmission rate (GTR) strongly depended on the polymer structure, gas type and temperature, with improvement in barrier performance for composite samples. Also, citral EO did not exert any weakening action on the tensile behavior. On the contrary, an increase of the elastic modulus and of the tensile strength was observed. Lastly, water contact angle measurements demonstrated the dependence of the film wettability on the content of citral EO.

The present paper describes the synthesis of novel bio-based poly(butylene 1,4-cyclohexane dicarboxylate)-containing random copolymers for sustainable and flexible packaging applications. On one side, the linear butylene moiety has been substituted by glycol subunits with alkyl pendant groups of different length. On the other side, copolymers with different cis / trans isomer ratio of cyclohexane rings have been synthesized. The prepared samples were subjected to molecular, thermal, diffractometric, and mechanical characterization. The barrier performances to O₂, CO₂, and N₂ gases were also evaluated. The presence of side alkyl groups did not alter the thermal stability, whereas it significantly influences the formation of ordered phases that deeply affect the functional properties, mainly in terms of mechanical response and barrier performance. In particular, the final materials present higher flexibility and significantly improved barrier properties with respect to the homopolymer and most polymers widely employed for flexible packaging. The improvement due to copolymerization was more pronounced in the case of higher co-unit-containing copolymers and for the samples with cyclohexane rings in the trans conformation.

Both academia and industry are currently devoting many efforts to develop high gas barrier bioplastics as substitutes of traditional fossil-based polymers. In this view, this contribution presents a new biobased aromatic polyester, i.e., poly(propylene 2,5-thiophenedicarboxylate) (PPTF), which has been compared with the furan-based counterpart (PPF). Both biopolyesters have been characterized from the molecular, thermo-mechanical and structural points of view. Gas permeability behavior has been evaluated with respect to 100% oxygen, carbon dioxide and nitrogen at 23 °C. In case of CO₂ gas test, gas transmission rate has been also measured at different temperatures. The permeability behavior at different relative humidity has been investigated for both biopolyesters, the thiophen-containing sample demonstrating to be better than the furan-containing counterpart. PPF's permeability behavior became worse than PPTF's with increasing RH, due to the more polar nature of the furan ring. Both biopolyesters under study are characterized by superior gas barrier performances with respect to PEF and PET. With the simple synthetic strategy adopted, the exceptional barrier properties render these new biobased polyesters interesting alternatives in the world of green and sustainable packaging materials. The different polarity and stability of heterocyclic rings was revealed to be an efficient tool to tailor the ability of crystallization, which in turn affects mechanical and barrier performances.

The chemical structure-dynamics relationship for poly(trimethylene 2,5-furanoate) and poly(trimethylene 1,4-cyclohexanedicarboxylate) was investigated via dielectric spectroscopy and compared with that of poly(trimethylene terephthalate) in order to evaluate the impact on the subglass dynamics of the chemical nature of the ring. Further comparison was accomplished with the neopentyl glycol containing counterparts: poly(neopentyl 2,5-furanoate) and poly(neopentyl 1,4-cyclohexanedicarboxylate). Our study reveals a multimodal nature of the subglass β process. For the more flexible polymers (containing cyclohexane rings) three modes for the β process were detected. The faster mode was assigned to the relaxation of the oxygen linked to the aliphatic carbon, the slower one to the link between the aliphatic ring and the ester group, and the third mode to the aliphatic ring. For stiffer polymers (containing aromatic rings), the local modes appear more coupled. This effect is more evident in the polymers with the furan ring where essentially a single β mode can be resolved.

Innovative nanofibrous scaffolds have attracted considerable attention in bone tissue engineering, due to their ability to mimic the hierarchical architecture of an extracellular matrix. Aiming at investigating how the polymer chemistry and fiber orientation of electrospun scaffolds (ES) based on poly(butylene succinate) (PBS) and poly(butylene succinate/diglycolate) (P(BS80BDG20)) affect human osteoblast differentiation, uniaxially aligned (a-) and randomly (r-) distributed nanofibers were produced. Although human osteoblastic SAOS-2 cells were shown to be viable and adherent onto all ES materials, a-P(BS80BDG20) exhibited the best performance both in terms of cellular phosphorylated focal adhesion kinase expression and in terms of alkaline phosphatase activity, calcified bone matrix deposition and quantitative gene expression of bone specific markers during differentiation. It has been hypothesized that the presence of ether linkages may lead to an increased density of hydrogen bond acceptors along the P(BS80BDG20) backbone, which, by interacting with cell membrane components, can in turn promote a better cell attachment on the copolymer mats with respect to the PBS homopolymer. Furthermore, although displaying the same chemical structure, r-P(BS80BDG20) scaffolds showed a reduced cell attachment and osteogenic differentiation in comparison with a-P(BS80BDG20), evidencing the importance of nanofiber alignment. Thus, the coupled action of polymer chemical structure and nanofiber alignment played a significant role in promoting the biological interaction.

Random copolymers of poly(propylene 1,4-cyclohexanedicarboxylate) containing different amounts of neopentyl glycol sub-unit were investigated from the gas barrier point of view at the standard temperature of analysis (23 °C) with respect to the three main gases used in food packaging field: N₂, O₂, and CO₂. The effect of temperature was also evaluated, considering two temperatures close to the T g sample (8 and 15 °C) and two above T g (30 and 38 °C). Barrier performances were checked after food contact simulants and in different relative humidity (RH) environments obtained with two saturated saline solutions (Standard Atmosphere, 23 °C, 85% of RH, with saturated KCl solution; Tropical Climate, 38 °C, 90% RH, with saturated KNO₃ solution). The results obtained were compared to those of untreated film, which was used as a reference. The relationships between the gas transmission rate, the diffusion coefficients, the solubility, and the copolymer composition were established. The results highlighted a correlation between barrier performance and copolymer composition and the applied treatment. In particular, copolymerization did not cause a worsening of the barrier properties, whereas the different treatments differently influenced the gas barrier behavior, depending on the chemical polymer structure. After treatment, Fourier transform infrared analysis confirmed the chemical stability of these copolymers. Films were transparent, with a light yellowish color, slightly more intense after all treatments.

α and β crystalline phases of poly(ethylene furanoate) (PEF) were determined using X-ray powder diffraction by structure resolution in direct space and Rietveld refinement. Moreover, the α' structure of a PEF sample was refined from data previously reported for PEF fiber. Triclinic α-PEF a = 5.729 Å, b = 7.89 Å, c = 9.62 Å, α = 98.1°, β = 65.1°, γ = 101.3°; monoclinic α'-PEF a = 5.912 Å, b = 6.91 Å, c = 19.73 Å, α = 90°, β = 90°, γ = 104.41°; and monoclinic β-PEF a = 5.953 Å, b = 6.60 Å, c = 10.52 Å, α = 90°, β = 107.0°, γ = 90° were determined as the best fitting of X-ray diffraction (XRD) powder patterns. Final atomic coordinates are reported for all polymorphs. In all cases PEF chains adopted an almost planar configuration., Competing Interests: The authors declare no conflict of interest.

Many efforts are currently devoted to the design and development of high performance bioplastics to replace traditional fossil-based polymers. In response, this contribution presents a new biobased aromatic polyester, i.e., poly(butylene 2,5-thiophenedicarboxylate) (PBTF). Here, PBTF is characterized from the molecular, thermo-mechanical and structural point of view. Gas permeability is evaluated at different temperatures, in the range below and above glass transition, providing a full insight into the performances of this material under different operating conditions, and demonstrating the superior gas barrier behavior of PBTF with respect to other polyesters, such as PEF and PET. The combination of calorimetric and diffractometric studies allows for a deep understanding of the structure of PBTF, revealing the presence of a not-induced 2D-ordered phase ( meso -phase), responsible for its outstanding gas permeability behavior. The simple synthetic strategy adopted, the exceptional barrier properties, combined with the interesting mechanical characteristics of PBTF open up new scenarios in the world of green and sustainable packaging materials., Competing Interests: The authors declare no conflict of interest.

In the last decade, there has been an increased interest from the food packaging industry toward the development and application of biodegradable and biobased plastics, to contribute to the sustainable economy and to reduce the huge environmental problem afflicting the planet. In this framework, the present paper describes the synthesis of novel PBS (poly(butylene succinate))-based random copolymers with different composition containing glycol sub-units characterized by alkyl pendant groups of different length. The prepared samples were subjected to molecular, thermal, diffractometric and mechanical characterization. The barrier performances to O₂, CO₂ and N₂ gases were also evaluated, envisioning for these new materials an application in food packaging. The presence of the side alkyl groups did not alter the thermal stability, whereas it significantly reduced the sample crystallinity degree, making these materials more flexible. The barrier properties were found to be worse than PBS; however, some of them were comparable to, or even better than, those of Low Density Polyethylene (LDPE), widely employed for flexible food packaging. The entity of variations in the final properties due to copolymerization were more modest in the case of the co -unit with short side methyl groups, which, when included in the PBS crystal lattice, causes a more modest decrement of crystallinity degree., Competing Interests: The authors declare no conflict of interest.

In the last decade, there has been an increased interest from the food packaging industry toward the development and application of bioplastics, to contribute to the sustainable economy and to reduce the huge environmental problem afflicting the planet. In the present work, we focus on a new furan-based polyester, poly(neopentyl glycol 2,5-furanoate) (PNF) to be used for sustainable food packaging applications. The aromatic polyester was successfully synthesized with high molecular weight, through a solvent-free process, starting directly from 2,5-furandicarboxylic acid. PNF was revealed to be a material with good thermal stability, characterized by a higher T g and T m and a lower RAF fraction compared to poly(propylene 2,5-furanoate) (PPF), ascribable to the two methyl side groups present in PNF glycol-sub-unit. PNF's mechanical characteristics, i.e., very high elastic modulus and brittle fracture, were found to be similar to those of PPF and PEF. Barrier properties to different gases, temperatures and relative humidity were evaluated. From the results obtained, PNF was showed to be a material with very smart barrier performances, significantly superior with respect to PEF's ones. Lastly, PNF's permeability behavior did not appreciably change after contact with food simulants, whereas it got worse with increasing RH, due to the polar nature of furan ring., Competing Interests: The authors declare no conflict of interest.

Biodegradable poly(butylene succinate) (PBS)-based random copolymers containing thioether linkages (P(BSxTDGSy)) of various compositions have been investigated and characterized from the gas barrier, thermal, and mechanical point of view, after food contact simulants or thermal and photoaging processes. Each stress treatment was performed on thin films and the results obtained have been compared to the same untreated film, used as a standard. Barrier properties with different gases (O₂ and CO₂) were evaluated, showing that the polymer chemical composition strongly influenced the permeability behavior. The relationships between the diffusion coefficients ( D ) and solubility ( S ) with polymer composition were also investigated. The results highlighted a correlation between polymer chemical structure and treatment. Gas transmission rate ( GTR ) mainly depending on the performed treatment, as GTR increased with the increase of TDGS co-unit amount. Thermal and mechanical tests allowed for the recording of variations in the degree of crystallinity and in the tensile properties. An increase in the crystallinity degree was recorded after contact with simulant liquids and aging treatments, together with a molecular weight decrease, a slight enhancement of the elastic modulus and a decrement of the elongation at break, proportional to the TDGS co-unit content., Competing Interests: The authors declare no conflict of interest.

A biodegradable and biocompatible electrospun scaffold with shape memory behavior in the physiological temperature range is here presented. It was obtained starting from a specifically designed, biobased PLLA-based triblock copolymer, where the central block is poly(propylene azelate-co-propylene sebacate) (P(PAz60PSeb40)) random copolymer. Shape memory properties are determined by the contemporary presence of the low melting crystals of the P(PAz60PSeb40) block, acting as switching segment, and of the high melting crystal phase of PLLA blocks, acting as physical network. It is demonstrated that a straightforward annealing process applied to the crystal phase of the switching element gives the possibility to tune the shape recovery temperature from about 25 to 50 °C, without the need of varying the copolymer's chemical structure. The thermal annealing approach here presented can be thus considered a powerful strategy for "ad hoc" programming the same material for applications requiring different recovery temperatures. Fibroblast culture experiments demonstrated scaffold biocompatibility.

EMG signals are often used to control prostheses or assistive devices, but have been rarely used in rehabilitation. We propose a novel approach to personalised rehabilitation, based on EMG-driven force field adaptation. As a step toward this direction, here we show how EMG activity and movement data during a robot-assisted motor task can be used to estimate muscle geometry. We compare three different models of muscle geometry, characterised by (i) constant moment arms (CM); (ii) a normative model, based on polynomial functions of joint angles with fixed coefficients (normative polynomial, NP); and (iii) a person-adaptive model, in which the same polynomial model is fitted to individual subjects data (fitted polynomial, FP). We found that the FP model has the best performance, specially for subjects whose size is farther from 'average'. The fitting results also emphasise the adverse effect of muscles co-contraction.

A new class of biodegradable materials developed by a combination of random eco-friendly copolyesters containing butylene succinate (BS) and triethylene succinate (TES) sequences with cellulose nanocrystals (CNC), is proposed and studied. Polymers and nanocomposite films were prepared by an optimized extrusion process to improve the processability and mechanical response for flexible film manufacturing. Poly(butylene succinate) (PBS) homopolymer and two random copolyesters containing different amounts of TES co-units, P(BS85TES15) and P(BS70TES30), were synthesized by melt polycondensation. The effect of TES and CNC presence and content on the microstructure, tensile properties, thermal characteristics and disintegration under composting conditions, as well as on the toughening mechanism of the blends was investigated. Material properties were modulated by varying the chemical composition. CNC were used as reinforcement additive and their effect is modulated by the interaction with the three polymeric matrices. The extruded films displayed tunable degradation rates, mechanical properties and wettability, and showed promising results for different industrial applications., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Bioactive scaffolds for tissue engineering call for demands on new materials which can enhance traditional biocompatibility requirements previously considered for clinical implantation. The current commercially available thermoplastic materials, such as poly(lactic acid) (PLA), poly(glycolic acid) (PGA), poly(ε-caprolactone) (PCL) and their copolymers, have been used to fabricate scaffolds for regenerative medicine. However, these polymers have limitations including lacking of broadly tuning mechanical and degradable properties, and activation of specific cell-scaffold interactions, which limit their further application in tissue engineering. In the present study, electrospun scaffolds were successfully fabricated from a new class of block poly(butylene succinate)-based (PBS-based) copolyesters containing either butylene thiodiglycolate (BTDG) or butylene diglycolate (BDG) sequences. The polyesters displayed tunable mechanical properties and hydrolysis rate depending on the molecular architecture and on the kind of heteroatom introduced along the polymer backbone. To investigate their potential for skeletal regeneration, human mesenchymal stromal cells (hMSCs) were cultured on the scaffolds in basic, osteogenic and chondrogenic media. Our results demonstrated that PBS-based copolyesters containing thio-ether linkages (i.e. BTDG segments) were more favorable for chondrogenesis of hMSCs than those containing ether linkages (i.e. BDG sequences). In contrast, PBS-based copolyesters containing ether linkages showed enhanced mineralization. Therefore, these new functional scaffolds might hold potential for osteochondral tissue engineering applications., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

A new class of biodegradable and biocompatible poly(butylene 1,4-cyclohexanedicarboxylate) based random copolymers are proposed for biomedical applications. The introduction of ether-oxygen containing BDG sequences along the PBCE macromolecular chain is expected to remarkably improve chain flexibility and surface hydrophilicity due to the presence of highly electronegative oxygen atoms. P(BCExBDGy) copolymers were synthesized by polycondensation. The homopolymer PBCE and three copolymers, namely (P(BCE70BDG30), P(BCE55BDG45) and P(BCE40BDG60)) were characterized from the molecular, thermal, structural and mechanical point of view. Hydrolytic degradation studies in the presence and absence of hog-pancreas lipase were performed under physiological conditions. To evaluate the diffusion profile of small molecules through the polymer matrix, the release behaviour of fluorescein isothiocyanate (FITC) was investigated. For biocompatibility studies, cell adhesion and proliferation of murine fibroblast (L929) and endocrine pancreatic (INS-1) cells were performed on each polymeric film. Results showed that solid-state properties can be tailored by simply varying copolymers' composition. Crystallinity degree and hydrophobicity significantly decreased with the increase of BDG co-unit mol%. Moreover, mechanical properties and biodegradability of PBCE, both depending on crystallinity degree, were remarkably improved: P(BCE40BDG60) showed an elastomeric behaviour with εb over 600% and, as regard to biodegradability, after 98days it lost over 60% of its initial weight if incubated in the presence of the pancreatic lipase. Lastly, the newly developed biomaterials resulted not cytotoxic with both types of cells and could be properly tailored for biomedical applications varying the content of BDG co-unit mol%., (© 2013.)

Radial symmetry is essential for the conventional view of the polymer spherulite microstructure. Typically it is assumed that, in the course of the spherulite morphogenesis, the lamellar crystals grow radially. Using submicron X-ray diffraction, it is shown that in banded spherulites of poly(propylene adipate) the crystals have the shape of a helix with flat-on crystals winding around a virtual cylinder of about 6 µm in diameter. The helix angle of 30° implies that the crystal growth direction is tilted away from the spherulite radius by this angle. The implications of the helical crystal shape contradict the paradigm of the spherulitic microstructure. The radial growth rate of such spherulites does not correspond to the crystal growth rate, but to the propagation rate of the virtual cylinder the ribbons wind around., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)