Biodegradable Natural Hydrogels for Tissue Engineering, Controlled Release, and Soil Remediation.

This article provides insights into hydrogels of the most promising biodegradable natural polymers and their mechanisms of degradation, highlighting the different possibilities of controlling hydrogel degradation rates. Since biodegradable hydrogels can be designed as scaffolding materials to mimic the physical and biochemical properties of natural tissues, these hydrogels have found widespread application in the field of tissue engineering and controlled release. In the same manner, their potential as water reservoirs, macro- and microelement carriers, or matrixes for the selective adsorption of pollutants make them excellent candidates for sustainable soil amendment solutions. Accordingly, this article summarizes the recent advances in natural biodegradable hydrogels in the fields of tissue engineering, controlled release, and soil remediation, emphasizing the new opportunities that degradability and its tunability offer for the design and applicability of hydrogels.

Assemblable 3D biomimetic microenvironment for hMSC osteogenic differentiation.

Adequate simulation mimicking a tissue's native environment is one of the elemental premises in tissue engineering. Although various attempts have been made to induce human mesenchymal stem cells (hMSC) into an osteogenic pathway, they are still far from widespread clinical application. Most strategies focus primarily on providing a specific type of cue, inadequately replicating the complexity of the bone microenvironment. An alternative multifunctional platform for hMSC osteogenic differentiation has been produced. It is based on poly(vinylidene fluoride) (PVDF) and cobalt ferrites magnetoelectric microspheres, functionalized with collagen and gelatin, and packed in a 3D arrangement. This platform is capable of performing mechanical stimulation of piezoelectric PVDF, mimicking the bones electromechanical biophysical cues. Surface functionalization with extracellular matrix biomolecules and osteogenic medium complete this all-round approach. hMSC were cultured in osteogenic inducing conditions and tested for proliferation, surface biomarkers, and gene expression to evaluate their osteogenic commitment.

AC/DC Magnetic Field Sensing Based on a Piezoelectric Polymer and a Fully Printed Planar Spiral Coil.

Additive manufacturing (AM) is emerging as an eco-friendly method for minimizing waste, as the demand for responsive materials in IoT and Industry 4.0 is on the rise. Magnetoactive composites, which are manufactured through AM, facilitate nonintrusive remote sensing and actuation. Printed magnetoelectric composites are an innovative method that utilizes the synergies between magnetic and electric properties. The study of magnetoelectric effects, including the recently validated piezoinductive effect, demonstrates the generation of electric voltage through external AC and DC magnetic fields. This shift in magnetic sensors, utilizing piezoinductive effect of the piezoelectric polymer poly(vinylidene fluoride), PVDF, eliminates the need for magnetic fillers in printed devices, aligning with sustainability principles, essential for the deployment of IoT and Industry 4.0. The achieved sensitivity surpasses other studies by 100 times, showcasing linear outputs for both applied AC and DC magnetic fields. Additionally, the sensor capitalizes on the linear phase shift of the generated signal with an applied DC magnetic field, an unprecedented effect. Thus, this work introduces a remarkable magnetoactive device with a sensitivity of ST = 95.1 ± 0.9 µV Oe-1 mT-1, a significantly improved performance compared to magnetoelectric devices using polymer composites. As a functional proof of concept of the developed system, a magnetic position sensor has been demonstrated.

Inkjet-Printed Bio-Based Melanin Composite Humidity Sensor for Sustainable Electronics.

A lack of sustainability in the design of electronic components contributes to the current challenges of electronic waste and material sourcing. Common materials for electronics are prone to environmental, economic, and ethical problems in their sourcing, and at the end of their life often contribute to toxic and nonrecyclable waste. This study investigates the inkjet printing of flexible humidity sensors and includes biosourced and biodegradable materials to improve the sustainability of the process. Humidity sensors are useful tools for monitoring atmospheric conditions in various fields. Here, an aqueous dispersion of black soldier fly melanin was optimized for printing with a cosolvent and deposited onto interdigitated silver electrodes on flexible substrates. Impedance spectroscopy demonstrated that adding choline chloride increased the ion concentration and AC conductivity by more than 3 orders of magnitude, resulting in a significant improvement in sensing performance and reduced hysteresis. The devices exhibit fast detection (0.8 ± 0.5 s) and recovery times (0.8 ± 0.3 s), with a 170 ± 40-fold decrease in impedance for relative humidity changes from 30% to 90%. This factor is lowered upon prolonged exposure to high humidity in tests over 72 h during which a stable operation is reached. The low embodied energy of the sensor, achieved through material-efficient deposition and the use of waste management byproducts, enhances its sustainability. In addition, approaches for reusability and degradability are presented, rendering the sensor suitable for wearable or agricultural applications.

Enhanced Electrochemiluminescence at the Gas/Liquid Interface of Bubbles Propelled into Solution.

Electrochemiluminescence (ECL) is typically confined to a micrometric region from the electrode surface. This study demonstrates that ECL emission can extend up to several millimeters away from the electrode employing electrogenerated chlorine bubbles. The mechanism behind this bubble-enhanced ECL was investigated using an Au microelectrode in chloride-containing and chloride-free electrolyte solutions. We discovered that ECL emission at the gas/solution interface is driven by two parallel effects. First, the bubble corona effect facilitates the generation of hydroxyl radicals capable of oxidizing luminol while the bubble is attached to the surface. Second, hypochlorite generated from chlorine sustains luminol emission for over 200 s and extends the emission range up to 5 mm into the solution, following bubble detachment. The new approach can increase the emission intensity of luminol-based assays 5-fold compared to the conventional method. This is demonstrated through a glucose bioassay, using a midrange mobile phone camera for detection. These findings significantly expand the potential applications of ECL by extending its effective range in time and space.

Cu2+-Assisted Synthesis of Ultrasharp and Sub-10 nm Gold Nanostars. Applications in Catalysis, Sensing, and Photothermia.

Gold nanostars have shown enormous potential as the main enablers of advanced applications ranging from biomedicine to sensing or catalysis. Their unique anisotropic structure featuring sharp spikes that grow from a central core offers enhanced optical capabilities and spectral tunability. Although several synthesis methods yield NSs of different morphologies and sizes up to several hundred nanometers, obtaining small NSs, while maintaining their plasmonic properties in the near-infrared, has proven challenging and elusive. Here, we show that Cu2+ addition during NS synthesis in polyvinylpyrrolidone/dimethylformamide generates more crystallographic defects and promotes the directional growth, giving rise to NSs with a larger number of much sharper spikes. They are also formed at smaller volumes, enabling the generation of ultrasmall nanostars, with a volume as small as 421 nm3 (i.e., 9.2 nm of volume-equivalent diameter), while maintaining a plasmon resonance in the near-infrared. To this end, we systematically evaluate the influence of synthesis parameters on the nanostar size and optical characteristics and demonstrate their properties for applications in catalysis, surface-enhanced Raman spectroscopy sensing, and hyperthermia. The ultrasmall nanostars show excellent attributes in all of them, leveraging their small size to enhance properties related to a higher surface-to-volume ratio or colloidal diffusivity.

Self-sensing magnetic actuator based on sustainable collagen hybrid nanocomposites.

Taking into account that natural polymers are renewable and biodegradable, hybrid materials based on natural polymers are required for advanced technological applications with reduced environmental footprint. In this work, sustainable composites have been developed based on collagen as a polymeric matrix and different magnetic fillers, in order to tailor magnetic response. The composites were prepared by solution casting with 30 wt% of magnetite nanoparticles (Fe3O4 NPs), magnetite nanorods (Fe3O4 NRs) or cobalt ferrite nanoparticles (CoFe2O4 NPs). It is shown that the magnetic filler type has no bearing on the morphology, physical-chemical, or thermal characteristics of the composites, whereas the mechanical properties are determined by the magnetic filler, leading to a reduction in tensile strength, with values of 4.95 MPa for Fe3O4 NPs, 9.20 MPa for Fe3O4 NRs and 5.21 MPa for CoFe2O4 NPs containing samples. However, the highest magnetization saturation is obtained for Fe3O4 NPs (44 emu.g-1) and the higher coercive field for CoFe2O4 NPs (2062 Oe). In order to prove functionality of the developed composites, a self-sensing magnetic actuator device has been developed with the composite film with CoFe2O4 NPs, showing high stability over cycling.

The surface charge of electroactive materials governs cell behaviour through its effect on protein deposition.

The precise mechanisms underlying the cellular response to static electric cues remain unclear, limiting the design and development of biomaterials that utilize this parameter to enhance specific biological behaviours. To gather information on this matter we have explored the interaction of collagen type-I, the most abundant mammalian extracellular protein, with poly(vinylidene fluoride) (PVDF), an electroactive polymer with great potential for tissue engineering applications. Our results reveal significant differences in collagen affinity, conformation, and interaction strength depending on the electric charge of the PVDF surface, which subsequently affects the behaviour of mesenchymal stem cells seeded on them. These findings highlight the importance of surface charge in the establishment of the material-protein interface and ultimately in the biological response to the material. STATEMENT OF SIGNIFICANCE: The development of new tissue engineering strategies relies heavily on the understanding of how biomaterials interact with biological tissues. Although several factors drive this process and their driving principles have been identified, the relevance and mechanism by which the surface potential influences cell behaviour is still unknown. In our study, we investigate the interaction between collagen, the most abundant component of the extracellular matrix, and poly(vinylidene fluoride) with varying surface charges. Our findings reveal substantial variations in the binding forces, structure and adhesion of collagen on the different surfaces, which collectively explain the differential cellular responses. By exposing these differences, our research fills a critical knowledge gap and paves the way for innovations in material design for advanced tissue regeneration strategies.

Sustainable Lignin-Reinforced Chitosan Membranes for Efficient Cr(VI) Water Remediation.

The pollution of aquatic environments is a growing problem linked to population growth and intense anthropogenic activities. Because of their potential impact on human health and the environment, special attention is paid to contaminants of emerging concern, namely heavy metals. Thus, this work proposes the use of naturally derived materials capable of adsorbing chromium (VI) (Cr(VI)), a contaminant known for its potential toxicity and carcinogenic effects, providing a sustainable alternative for water remediation. For this purpose, membranes based on chitosan (CS) and chitosan/Kraft lignin (CS/KL) with different percentages of lignin (0.01 and 0.05 g) were developed using the solvent casting technique. The introduction of lignin imparts mechanical strength and reduces swelling in pristine chitosan. The CS and CS/0.01 KL membranes performed excellently, removing Cr(VI) at an initial 5 mg/L concentration. After 5 h of contact time, they showed about 100% removal. The adsorption process was analyzed using the pseudo-first-order model, and the interaction between the polymer matrix and the contaminant was attributed to electrostatic interactions. Therefore, CS and CS/KL membranes could be low-cost and efficient adsorbents for heavy metals in wastewater treatment applications.

Towards Sustainable Temperature Sensor Production through CO2-Derived Polycarbonate-Based Composites.

The steep increase in carbon dioxide (CO2) emissions has created great concern due to its role in the greenhouse effect and global warming. One approach to mitigate CO2 levels involves its application in specific technologies. In this context, CO2 can be used for a more sustainable synthesis of polycarbonates (CO2-PCs). In this research, CO2-PC films and composites with multiwalled carbon nanotubes (MWCNTs, ranging from 0.2 to 7.0 wt.%) have been prepared to achieve more sustainable multifunctional sensing devices. The inclusion of the carbonaceous fillers allows for the electrical conductivity to be enhanced, reaching the percolation threshold (Pc) at 0.1 wt.% MWCNTs and a maximum electrical conductivity of 0.107 S·m-1 for the composite containing 1.5 wt.% MWCNTs. The composite containing 3.0 wt.% MWCNTs was also studied, showing a stable and linear response under temperature variations from 40 to 100 °C and from 30 to 45 °C, with a sensitivity of 1.3 × 10-4 °C-1. Thus, this investigation demonstrates the possibility of employing CO2-derived PC/MWCNT composites as thermoresistive sensing materials, allowing for the transition towards sustainable polymer-based electronics.

Metal-Organic Frameworks for Dual Photo-Oxidation and Capture of Arsenic from Water.

Despite rapid technological progress, heavy metal water pollution, and particularly arsenic contamination, remains a significant global challenge. In addition, the stabilization of trivalent arsenic as neutral arsenite (AsIII) species hinders its removal by conventional sorbents. While adsorption of anionic arsenate (AsV) species is in principle more feasible, there are only few adsorbents capable of adsorbing both forms of arsenic. In this work, we explore the potential of two well-known families of Metal-Organic Frameworks (MOFs), UiO-66 and MIL-125, to simultaneously adsorb and photo-oxidize arsenic species from water. Our results demonstrate that the formation of AsV ions upon light irradiation promotes the subsequent adsorption of AsIII species. Thus, we propose the combined utilization of photocatalysis and adsorption with Metal-Organic Framework photocatalysts for water remediation purposes.

Improving Definition of Screen-Printed Functional Materials for Sensing Application.

Screen printing is one of the most used techniques for developing printed electronics. It stands out for its simplicity, scalability, and effectivity. Specifically, the manufacturing of hybrid integrated circuits has promoted the development of the technique, and the photovoltaic industry has enhanced the printing process by developing high-performance metallization pastes and high-end screens. In recent years, fine lines of 50 µm or smaller are about to be adopted in mass production, and screen printing has to compete with digital printing techniques such as inkjet printing, which can reach narrower lines. In this sense, this work is focused on testing the printing resolution of a high-performance stainless-steel screen with commercial conductive inks and functional lab-made inks based on reduced graphene oxide using an interdigitated structure. We achieved electrically conductive functional patterns with a minimum printing resolution of 40 µm for all inks.

Sonophotocatalytic removal of organic dyes in real water environments using reusable BiSI@PVDF-HFP nanocomposite membranes.

Focusing on the uncontrolled discharge of organic dyes, a known threat to human health and aquatic ecosystems, this work employs a dual-functional catalyst approach, by immobilizing a synthesized bismuth sulfur iodide (BiSI) into a poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) polymeric matrix for multifunctional water remediation. The resulting BiSI@PVDF nanocomposite membrane (NCM), with 20 wt% filler content, maintains a highly porous structure without compromising morphology or thermal properties. Demonstrating efficiency in natural pH conditions, the NCM removes nearly all Rhodamine B (RhB) within 1 h, using a combined sonophotocatalytic process. Langmuir and pseudo-second-order models describe the remediation process, achieving a maximum removal capacity (Qmax) of 72.2 mg/g. In addition, the combined sonophotocatalysis achieved a degradation rate ten and five times higher (0.026 min-1) than photocatalysis (0.002 min-1) and sonocatalysis (0.010 min-1). Furthermore, the NCM exhibits notable reusability over five cycles without efficiency losses and efficiencies always higher than 90%, highlighting its potential for real water matrices. The study underscores the suitability of BiSI@PVDF as a dual-functional catalyst for organic dye degradation, showcasing synergistic adsorption, photocatalysis, and sonocatalysis for water remediation.

Materials and Strategies to Enhance Melt Electrowriting Potential.

Melt electrowriting (MEW) is an emerging additive manufacturing (AM) technology that enables the precise deposition of continuous polymeric microfibers, allowing for the creation of high-resolution constructs. In recent years, MEW has undergone a revolution, with the introduction of active properties or additional functionalities through novel polymer processing strategies, the incorporation of functional fillers, postprocessing, or the combination with other techniques. While extensively explored in biomedical applications, MEW's potential in other fields remains untapped. Thus, this review explores MEW's characteristics from a materials science perspective, emphasizing the diverse range of materials and composites processed by this technique and their current and potential applications. Additionally, the prospects offered by postprinting processing techniques are explored, together with the synergy achieved by combining melt electrowriting with other manufacturing methods. By highlighting the untapped potentials of MEW, this review aims to inspire research groups across various fields to leverage this technology for innovative endeavors.

Strategies for Improving Sustainability in the Development of High-Performance Styrenic Block Copolymers by Developing Blends with Cellulose Derivatives.

Next-generation high-performance polymers require consideration as sustainable solutions. Here, to satisfy these criteria, we propose to combine high-performance styrenic block copolymers, a class of thermoplastic elastomer, with cellulose derivatives as a reinforcing agent with the aim of maintaining and/or improving structural and surface properties. A great advantage of the proposed blends is, besides their biocompatibility, a decrease in environmental impact due to blending with a natural polymer. Particularly, we focus on identifying the effect of different blending compounds and blend ratios on the morphological, structural, thermal, mechanical, electrical and cytotoxic characteristics of materials. This research provides, together with novel material formulations, practical guidelines for the design and fabrication of next-generation sustainable high-performance polymers.

Ionic Thermoelectric Generators in Vertical and Planar Topologies Based on Fluorinated Polymer Hybrid Materials with Ionic Liquids.

Ionic thermoelectrics (TEs), in which voltage generation is based on ion migration, are suitable for applications based on their low cost, high flexibility, high ionic conductivity, and wide range of Seebeck coefficients. This work reports on the development of ionic TE materials based on the poly(vinylidene fluoride-trifluoroethylene), Poly(VDF-co-TrFE), as host polymer blended with different contents of the ionic liquid, IL, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [EMIM][TFSI]. The morphology, physico-chemical, thermal, mechanical, and electrical properties of the samples are evaluated together with the TE response. It is demonstrated that the IL acts as a nucleating agent for polymer crystallization. The mechanical properties and ionic conductivity values are dependent on the IL content. A high room temperature ionic conductivity of 0.008 S cm-1 is obtained for the sample with 60 wt% of [EMIM][TFSI] IL. The TE properties depend on both IL content and device topology-vertical or planar-the largest generated voltage range being obtained for the planar topology and the sample with 10 wt% of IL content, characterized by a Seebeck coefficient of 1.2 mV K-1. Based on the obtained maximum power density of 4.9 µW m-2, these materials are suitable for a new generation of TE devices.

In vitro neuronal and glial response to magnetically stimulated piezoelectric poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV)/cobalt ferrite (CFO) microspheres.

Polymer biomaterials are being considered for tissue regeneration due to the possibility of resembling different extracellular matrix characteristics. However, most current scaffolds cannot respond to physical-chemical modifications of the cell microenvironment. Stimuli-responsive materials, such as electroactive smart polymers, are increasingly gaining attention once they can produce electrical potentials without external power supplies. The presence of piezoelectricity in human tissues like cartilage and bone highlights the importance of electrical stimulation in physiological conditions. Although poly(vinylidene fluoride) (PVDF) is one of the piezoelectric polymers with the highest piezoelectric response, it is not biodegradable. Poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) is a promising copolymer of poly(hydroxybutyrate) (PHB) for tissue engineering and regeneration applications. It offers biodegradability, piezoelectric properties, biocompatibility, and bioactivity, making it a superior option to PVDF for biomedical purposes requiring biodegradability. Magnetoelectric polymer composites can be made by combining magnetostrictive particles and piezoelectric polymers to further tune their properties for tissue regeneration. These composites convert magnetic stimuli into electrical stimuli, generating local electrical potentials for various applications. Cobalt ferrites (CFO) and piezoelectric polymers have been combined and processed into different morphologies, maintaining biocompatibility for tissue engineering. The present work studied how PHBV/CFO microspheres affected neural and glial response in spinal cord cultures. It is expected that the electrical signals generated by these microspheres due to their magnetoelectric nature could aid in tissue regeneration and repair. PHBV/CFO microspheres were not cytotoxic and were able to impact neurite outgrowth and promote neuronal differentiation. Furthermore, PHBV/CFO microspheres led to microglia activation and induced the release of several bioactive molecules. Importantly, magnetically stimulated microspheres ameliorated cell viability after an in vitro ROS-induced lesion of spinal cord cultures, which suggests a beneficial effect on tissue regeneration and repair.

State of the Art and Current Challenges on Electroactive Biomaterials and Strategies for Neural Tissue Regeneration.

The loss or failure of an organ/tissue stands as one of the healthcare system's most prevalent, devastating, and costly challenges. Strategies for neural tissue repair and regeneration have received significant attention due to their particularly strong impact on patients' well-being. Many research efforts are dedicated not only to control the disease symptoms but also to find solutions to repair the damaged tissues. Neural tissue engineering (TE) plays a key role in addressing this problem and significant efforts are being carried out to develop strategies for neural repair treatment. In the last years, active materials allowing to tune cell-materials interaction are being increasingly used, representing a recent paradigm in TE applications. Among the most important stimuli influencing cell behavior are the electrical and mechanical ones. In this way, materials with the ability to provide this kind of stimuli to the neural cells seem to be appropriate to support neural TE. In this scope, this review summarizes the different biomaterials types used for neural TE, highlighting the relevance of using active biomaterials and electrical stimulation. Furthermore, this review provides not only a compilation of the most relevant studies and results but also strategies for novel and more biomimetic approaches for neural TE.

Cryo-Electrohydrodynamic Jetting of Aqueous Silk Fibroin Solutions.

The incorporation of 3D-printing principles with electrohydrodynamic (EHD) jetting provides a harmonious balance between resolution and processing speed, allowing for the creation of high-resolution centimeter-scale constructs. Typically, EHD jetting of polymer melts offers the advantage of rapid solidification, while processing polymer solutions requires solvent evaporation to transition into solid fibers, creating challenges for reliable printing. This study navigates a hybrid approach aimed at minimizing printing instabilities by combining viscous solutions and achieving rapid solidification through freezing. Our method introduces and fully describes a modified open-source 3D printer equipped with a frozen collector that operates at -35 °C. As a proof of concept, highly concentrated silk fibroin aqueous solutions are processed into stable micrometer scale jets, which rapidly solidify upon contact with the frozen collector. This results in the formation of uniform microfibers characterized by an average diameter of 27 ± 5 µm, a textured surface, and porous internal channels. The absence of instabilities and the notably fast direct writing speed of 42 mm·s-1 enable precise, fast, and reliable deposition of these fibers into porous constructs spanning several centimeters. The effectiveness of this approach is demonstrated by the consistent production of biologically relevant scaffolds that can be customized with varying pore sizes and shapes. The achieved degree of control over micrometric jet solidification and deposition dynamics represents a significant advancement in EHD jetting, particularly within the domain of aqueous polymer solutions, offering new opportunities for the development of intricate and functional biological structures.

Biodegradable and biocompatible collagen-based hybrid materials for force sensing applications.

With the aim of replacing synthetic macromolecules by biological macromolecules for advanced applications, collagen films were produced with two different ionic liquids (ILs), choline dihydrogen phosphate ([Ch][DHP]) and choline serinate ([Ch][Seri]), added in order to modulate the electrical responses. The films were prepared by casting, varying IL content between 0 and 6 wt%. The morphology and thermal properties of the resulting films were found to be independent of both IL type and content. However, the highest direct curret (d.c.) electrical conductivity (1.4 × 10-8 S·cm-1) was achieved for collagen films containing 3 wt% [Ch][DHP]. Furthermore, it was demonstrated that IL/collagen films were non-cytotoxic, with cell activity values exceeding 70 %. These collagen films were proven to be suitable for force sensing applications, displaying excellent sensitivity and stability upon repeated testing.