Sustainable Polymeric Biomaterials from Alternative Feedstocks.

As materials engineered to interact with biological systems for medical purposes, polymeric biomedical materials have revolutionized and are indispensable in modern healthcare. However, aging populations and improving healthcare standards worldwide have resulted in ever-increasing demands for such biomaterials. Currently, many clinically used polymers are derived from nonrenewable petroleum resources, thus spurring the need for exploring alternatives for the next generation of sustainable biomaterials. Other than biomass, this Perspective also spotlights carbon dioxide and postuse plastics as viable resources potentially suitable for biomaterial production. For each alternative feedstock, key recent developments and practical considerations are discussed, including emerging biomaterial applications, possible feedstock sources, and hindrances toward translation and practical adoption. Other than replacements for petroleum-derived polymers, we explore how utilization of these alternatives capitalizes on their intrinsic physiochemical and material properties to achieve their desired therapeutic effects. We hope that this Perspective can stimulate further development in sustainable biomaterials to achieve practical therapeutic benefits as part of a circular materials economy with minimal environmental impact.

Baiting bacteria with amino acidic and peptidic corona coated defect-engineered antimicrobial nanoclusters for optimized wound healing.

Keeping steps ahead of the bacteria in the race for more efficacious antibacterial strategies is increasingly difficult with the advent of bacterial resistance genes. Herein, we engineered copper sulfide nanoclusters (CuSx NCs) with variable sulfur defects for enhanced dual-treatment of bacterial infections by manipulating photothermal effects and Fenton-like activity. Next, by encasing CuSx NCs with a complex mixture of amino acids and short peptides derived from Luria-Bertani bacterial culture media as a protein corona, we managed to coax E. Coli to take up these CuSx NCs. As a whole, Amino-Pep-CuSx NCs was perceived as a food source and actively consumed by bacteria, enhancing their effective uptake by at least 1.5-fold greater than full length BSA protein BSA-corona CuSx NCs. Through strategically using defect-engineering, we successfully fine-tune photothermal effect and Fenton-like capacity of CuSx NCs. Increased sulfur defects lead to reduced but sufficient heat generation under solar-light irradiation and increased production of toxic hydroxyl radicals. By fine-tuning sulfur defects during synthesis, we achieve CuSx NCs with an optimal synergistic effect, significantly enhancing their bactericidal properties. These ultra-small and biodegradable CuSx NCs can rapidly break down after treatment for clearance. Thus, Amino-Pep-CuSx NCs demonstrate effective eradication of bacteria both in vitro and in vivo because of their relatively high uptake, optimal balanced photothermal and chemodynamic outcomes. Our study offers a straightforward and efficient method to enhance bacterial uptake of next generation of antibacterial agents.

Bioaerosol Inactivation by a Cold Plasma Ionizer Coupled with an Electrostatic Precipitator.

Despite best efforts in air purification, airborne infectious diseases will continue to spread due to the continuous emission of bioaerosols by the host/infected person. Hence, a shift in focus from air purification to bioaerosol inactivation is urgently needed. To explore the potential of the cold plasma technology for preventing rapid spread of airborne infectious diseases, we studied a cold plasma ionizer (CPI) device and an electrostatic precipitator (ESP)-coupled CPI (CPI-ESP) device for the inactivation and cleaning of surface-spread microorganisms and bioaerosols, using porcine respiratory coronavirus (PRCV), Escherichia coli (E. coli), and aerosolized E. coli as representatives. We firstly demonstrated that CPI coupled with ESP is an effective technology for inactivating virus and bacteria spread on surfaces in an in-house test chamber. We then demonstrated the efficacy of CPI-coupled ESP for the inactivation of aerosolized E. coli in the same chamber. Furthermore, we have demonstrated the efficiency of a CPI-ESP coupled device for the inactivation of naturally occurring airborne microbials in a few indoor settings (i.e., a living room, a discussion room, a schoolroom, and an office) to determine the treatment duration- and human activity-dependent efficacy. To understand the disinfection mechanism, we conducted a fluorescence microscopy study to reveal different degrees of E. coli bacteria cell membrane damage under CPI treatment.

A Recyclable Ionogel with High Mechanical Robustness Based on Covalent Adaptable Networks.

Ionogels are an emerging class of soft materials for flexible electronics, with high ionic conductivity, low volatility, and mechanical stretchability. Recyclable ionogels are recently developed to address the sustainability crisis of current electronics, through the introduction of non-covalent bonds. However, this strategy sacrifices mechanical robustness and chemical stability, severely diminishing the potential for practical application. Here, covalent adaptable networks (CANs) are incorporated into ionogels, where dynamic covalent crosslinks endow high strength (11.3 MPa tensile strength), stretchability (2396% elongation at break), elasticity (energy loss coefficient of 0.055 at 100% strain), and durability (5000 cycles of 150% strain). The reversible nature of CANs allows the ionogel to be closed-loop recyclable for up to ten times. Additionally, the ionogel is toughened by physical crosslinks between conducting ions and polymer networks, breaking the common dilemma in enhancing mechanical properties and electrical conductivity. The ionogel demonstrates robust strain sensing performance under harsh mechanical treatments and is applied for reconfigurable multimodal sensing based on its recyclability. This study provides insights into improving the mechanical and electrical properties of ionogels toward functionally reliable and environmentally sustainable bioelectronics.

Muscle-Inspired Formable Wood-Based Phase Change Materials.

Phase change materials (PCMs) are crucial for sustainable thermal management in energy-efficient construction and cold chain logistics, as they can store and release renewable thermal energy. However, traditional PCMs suffer from leakage and a loss of formability above their phase change temperatures, limiting their shape stability and versatility. Inspired by the muscle structure, formable PCMs with a hierarchical structure and solvent-responsive supramolecular networks based on polyvinyl alcohol (PVA)/wood composites are developed. The material, in its hydrated state, demonstrates low stiffness and pliability due to the weak hydrogen bonding between aligned wood fibers and PVA molecules. Through treatment of poly(ethylene glycol) (PEG) into the PVA/wood PEG gel (PEG/PVA/W) with strengthened hydrogen bonds, the resulting wood-based PCMs in the hard and melting states elevate the tensile stress from 10.14 to 80.86 MPa and the stiffness from 420 MPa to 4.8 GPa, making it 530 times stiffer than the PEG/PVA counterpart. Capable of morphing in response to solvent changes, these formable PCMs enable intricate designs for thermal management. Furthermore, supported by a comprehensive life cycle assessment, these shape-adaptable, recyclable, and biodegradable PCMs with lower environmental footprint present a sustainable alternative to conventional plastics and thermal management materials.

In Situ Characterization Techniques for Electrochemical Nitrogen Reduction Reaction.

The electrochemical reduction of nitrogen to produce ammonia is pivotal in modern society due to its environmental friendliness and the substantial influence that ammonia has on food, chemicals, and energy. However, the current electrochemical nitrogen reduction reaction (NRR) mechanism is still imperfect, which seriously impedes the development of NRR. In situ characterization techniques offer insight into the alterations taking place at the electrode/electrolyte interface throughout the NRR process, thereby helping us to explore the NRR mechanism in-depth and ultimately promote the development of efficient catalytic systems for NRR. Herein, we introduce the popular theories and mechanisms of the electrochemical NRR and provide an extensive overview on the application of various in situ characterization approaches for on-site detection of reaction intermediates and catalyst transformations during electrocatalytic NRR processes, including different optical techniques, X-ray-based techniques, electron microscopy, and scanning probe microscopy. Finally, some major challenges and future directions of these in situ techniques are proposed.

Exploring Stimuli-Responsive Natural Processes for the Fabrication of High-Performance Materials.

Climate change and environmental pollution have underscored the urgency for more sustainable alternatives in synthetic polymer production. Nature's repertoire of biopolymers with excellent multifaceted properties alongside biodegradability could inspire next-generation innovative green polymer fabrication routes. Stimuli-induced processing, driven by changes in environmental factors, such as pH, ionic strength, and mechanical forces, plays a crucial role in natural polymeric self-assembly process. This perspective aims to close the gap in understanding biopolymer formation by highlighting the essential role of stimuli triggers in facilitating the bottom-up fabrication, allowing for the formation of intricate hierarchical structures. In particular, this perspective will delve into the stimuli-responsive processing of high-performance biopolymers produced by mussels, caddisflies, velvet worms, sharks, whelks, and squids, which are known for their robust mechanical properties, durability, and wet adhesion capabilities. Finally, we provide an overview of current advancements and challenges in understanding stimuli-induced natural formation pathways and their translation to biomimetic materials.

Adhesion Evolution: Designing Smart Polymeric Adhesive Systems with On-Demand Reversible Switchability.

Smart polymeric switchable adhesives represent a rapidly emerging class of advanced materials, exhibiting the ability to undergo on-demand transitioning between "On" and "Off" adhesion states. By selectively tuning external stimuli triggers (including temperature, light, electricity, magnetism, and chemical agents), we can engineer these materials to undergo reversible changes in their bonding capabilities. The strategic design selection of stimuli is a pivotal factor in the design of switchable adhesive systems. This review outlines recent advancements in the field of smart switchable polymeric adhesives over the past decade with a focus on the selection of stimulus triggers. These systems are further categorized into one of four adhesion switching mechanisms upon initiation by a specific stimuli-trigger: (i) interfacial adhesion, (ii) stiffness, (iii) contact area, or (iv) suction-based switching. Evaluation of adhesion switching performance across systems is primarily made based on three key metrics: (i) maximum adhesion strength, (ii) switch ratio, and (iii) switch time. Different stimuli and mechanisms offer distinct advantages and limitations, influencing the performance characteristics and applicability of these materials across domains such as detachable biomedical devices, robotic grippers, and climbing robots. This review thus offers a perspective on the present advancements and challenges in this emerging field, along with insights into future directions.

Pyrolytic Depolymerization of Polyolefins Catalysed by Zirconium-based UiO-66 Metal-Organic Frameworks.

Polyolefins such as polyethylenes and polypropylenes are the most-produced plastic waste globally, yet are difficult to convert into useful products due to their unreactivity. Pyrolysis is a practical method for large-scale treatment of mixed, contaminated plastic, allowing for their conversion into industrially-relevant petrochemicals. Metal-organic frameworks (MOFs), despite their tremendous utility in heterogeneous catalysis, have been overlooked for polyolefin depolymerization due to their perceived thermal instabilities and inability of polyethylenes and polypropylenes to penetrate their pores. Herein, we demonstrate the viability of UiO-66 MOFs containing coordinatively-unsaturated zirconium nodes, as effective catalysts for pyrolysis that significantly enhances the yields of valuable liquid and gas hydrocarbons, whilst halving the amounts of residual solids produced. Reactions occur on the Lewis-acidic UiO-66 nodes, without the need for noble metals, and yield aliphatic product distributions distinctly different from the aromatic-rich hydrocarbons that can be obtained from zeolite catalysis. We also demonstrate the first unambiguous characterization of polyolefin penetration into UiO-66 pores at pyrolytic temperatures, allowing access to the abundant Zr-oxo nodes within the MOF interior for efficient C-C cleavage. Our work highlights the potential of MOFs as highly-designable heterogeneous catalysts for depolymerisation of plastics, which can complement conventional catalysts in reactivity.

Light Switchable Bioorthogonal Reaction Manifold for Modulation of Hydrogel Properties.

Chemical reaction systems that can occur via multiple pathways in a controllable fashion are highly attractive for advanced materials applications and biological research. In this report, we introduce a bioorthogonal reaction manifold based on a chalcone pyrene (CPyr) moiety that can undergo either red-shifted photoreversible [2 + 2] cycloaddition or thiol-Michael addition click reaction. By coupling the CPyr to a water-soluble poly(ethylene glycol) end group, we demonstrate the efficient polymer dimerization and cleavage by blue light (λ = 450 nm) and UV light (λ = 340 nm), respectively. In the absence of light, CPyr rapidly reacts with thiols in aqueous environments, enabling fast and efficient polymer end-group functionalization. The chemical reaction manifold was further employed in polymer cross-linking for the preparation of hydrogels whose stiffness and morphology can be modulated by different photonic fields or the addition of a thiol cross-linker. The photoreversible cycloaddition and thiol-Michael addition click reaction can be used in conjunction for spatial and temporal conjugation of a streptavidin protein. Both cross-linking conditions are nontoxic to various cell lines, highlighting their potential in biomaterials applications.

Polyurea-urethane Temperature-responsive Hydrogels for Sustained Delivery of Anti-VEGF Therapeutics.

Temperature-responsive hydrogels, or thermogels, have emerged as a leading platform for sustained delivery of both small molecule drugs and macromolecular biologic therapeutics. Although thermogel properties can be modulated by varying the polymer's hydrophilic-hydrophobic balance, molecular weight and degree of branching, varying the supramolecular donor-acceptor interactions on the polymer remains surprisingly overlooked. Herein, to study the influence of enhanced hydrogen bonding on thermogelation, we synthesized a family of amphiphilic polymers containing urea and urethane linkages using quinuclidine as an organocatalyst. Our findings showed that the presence of strongly hydrogen bonding urea linkages significantly enhanced polymer hydration in water, in turn affecting hierarchical polymer self-assembly and macroscopic gel properties such as sol-gel phase transition temperature and gel stiffness. Additionally, analysis of the sustained release profiles of Aflibercept, an FDA-approved protein biologic for anti-angiogenic treatment, showed that urea bonds on the thermogel were able to significantly alter the drug release mechanism and kinetics compared to usage of polyurethane gels of similar composition and molecular weight. Our findings demonstrate the unrealized possibility of modulating gel properties and outcomes of sustained drug delivery through judicious variation of hydrogen bonding motifs on the polymer structure.

Electrospun PEO/PEG fibers as potential flexible phase change materials for thermal energy regulation.

Polyethylene glycol (PEG) is widely used as phase change materials (PCM) due to their versatile working temperature and high latent heat. However, the low molecular weight of PEG prevents from the formation of flexible microfibers, and the common leakage problem associated with solid-liquid PCM further hinders their applications in various fields. To address these challenges, polyethylene oxide (PEO) is incorporated as the supporting matrix for PEG, leading to a successful electrospinning of fibrous mats. Due to the similar chemical nature of both PEG and PEO, the blended composites show great compatibility and produce uniform electrospun fibers. The thermal properties of these fibers are characterized by DSC and TGA, and supercooling for the PEG(1050) component is effectively reduced by 75-85%. The morphology changes before and after leakage test are analyzed by SEM. Tensile and DMA tests show that the presence of PEG(1050) component contributes to plasticization effect, improving mechanical and thermomechanical strength. The ratio of PEO(600K):PEG(1050) at 7:3 affords the optimal performance with good chemical and form-stability, least shrinkage, and uniformity. These fibrous mats have potential applications in areas of food packaging, flexible wearable devices, or textiles to aid in thermal regulation.

Rapid-Response Water-Shrink Films with High Output Work Density Based on Polyethylene Oxide and α-Cyclodextrin for Autonomous Wound Closure.

Conventional wound closure methods, including sutures and tissue adhesives, present significant challenges for self-care treatment, particularly in the context of bleeding wounds. Existing stimuli-responsive contractile materials designed for autonomous wound closure frequently lack sufficient output work density to generate the force needed to bring the wound edges into proximity or necessitate stimuli that are not compatible with the human body. Here, semi-transparent, flexible, and water-responsive shrinkable films, composed of poly(ethylene oxide) and α-cyclodextrin, are reported. These films exhibit remarkable stability under ambient conditions and demonstrate significant contraction (≈50%) within 6 s upon exposure to water, generating substantial contractile stress (up to 6 MPa) and output work density (≈1028 kJ m-3), which is 100 times larger than that of conventional hydrogel and 25 times larger than that of skeletal muscles. Remarkably, upon hydration, these films are capable of lifting objects 10 000 times their own weight. Leveraging this technology, water-shrink tapes, which, upon contact with water, effectively constrict human skin and autonomously close bleeding wounds in animal models within 10 seconds, are developed further. This work offers a novel approach to skin wound management, showing significant potential for emergency and self-care scenarios.

White light powered antimicrobial nanoagents for triple photothermal, chemodynamic and photodynamic based sterilization.

Antibacterial nanoagents have been increasingly developed due to their favorable biocompatibility, cost-effective raw materials, and alternative chemical or optical properties. Nevertheless, there is still a pressing need for antibacterial nanoagents that exhibit outstanding bacteria-binding capabilities and high antibacterial efficiency. In this study, we constructed a multifunctional cascade bioreactor (GCDCO) as a novel antibacterial agent. This involved incorporating carbon dots (CDs), cobalt sulfide quantum dots (CoSx QDs), and glucose oxidase (GOx) to enhance bacterial inhibition under sunlight irradiation. The GCDCO demonstrated highly efficient antibacterial capabilities attributed to its favorable photothermal properties, photodynamic activity, as well as the synergistic effects of hyperthermia, glucose-augmented chemodynamic action, and additional photodynamic activity. Within this cascade bioreactor, CDs played the role of a photosensitizer for photodynamic therapy (PDT), capable of generating ˙O2- even under solar light irradiation. The CoSx QDs not only functioned as a catalytic component to decompose hydrogen peroxide (H2O2) and generate hydroxyl radicals (˙OH), but they also served as heat generators to enhance the Fenton-like catalysis process. Furthermore, GOx was incorporated into this cascade bioreactor to internally supply H2O2 by consuming glucose for a Fenton-like reaction. As a result, GCDCO could generate a substantial amount of reactive oxygen species (ROS), leading to a significant synergistic effect that greatly induced bacterial death. Furthermore, the in vitro antibacterial experiment revealed that GCDCO displayed notably enhanced antibacterial activity against E. coli (99+ %) when combined with glucose under simulated sunlight, surpassing the efficacy of the individual components. This underscores its remarkable efficiency in combating bacterial growth. Taken together, our GCDCO demonstrates significant potential for use in the routine treatment of skin infections among diabetic patients.

Electrical Control Grain Dimensionality with Multilevel Magnetic Anisotropy.

In alignment with the increasing demand for larger storage capacity and longer data retention, the electrical control of magnetic anisotropy has been a research focus in the realm of spintronics. Typically, magnetic anisotropy is determined by grain dimensionality, which is set during the fabrication of magnetic thin films. Despite the intrinsic correlation between magnetic anisotropy and grain dimensionality, there is a lack of experimental evidence for electrically controlling grain dimensionality, thereby impairing the efficiency of magnetic anisotropy modulation. Here, we demonstrate an electric field control of grain dimensionality and prove it as the active mechanism for tuning interfacial magnetism. The reduction in grain dimensionality is associated with a transition from ferromagnetic to superparamagnetic behavior. We achieve a nonvolatile and reversible modulation of the coercivity in both the ferromagnetic and superparamagnetic regimes. Subsequent electrical and elemental analysis confirms the variation in grain dimensionality upon the application of gate voltages, revealing a transition from a multidomain to a single-domain state, accompanied by a reduction in grain dimensionality. Furthermore, we exploit the influence of grain dimensionality on domain wall motion, extending its applicability to multilevel magnetic memory and synaptic devices. Our results provide a strategy for tuning interfacial magnetism through grain size engineering for advancements in high-performance spintronics.

Hydrogel for light delivery in biomedical applications.

Traditional optical waveguides or mediums are often silica-based materials, but their applications in biomedicine and healthcare are limited due to the poor biocompatibility and unsuitable mechanical properties. In term of the applications in human body, a biocompatible hydrogel system with excellent optical transparency and mechanical flexibility could be beneficial. In this review, we explore the different designs of hydrogel-based optical waveguides derived from natural and synthetic sources. We highlighted key developments such as light emitting contact lenses, implantable optical fibres, biosensing systems, luminating and fluorescent materials. Finally, we expand further on the challenges and perspectives for hydrogel waveguides to achieve clinical applications.

Bio-Polyethylene and Polyethylene Biocomposites: An Alternative toward a Sustainable Future.

Polyethylene (PE), a highly prevalent non-biodegradable polymer in the field of plastics, presents a waste management issue. To alleviate this issue, bio-based PE (bio-PE), derived from renewable resources like corn and sugarcane, offers an environmentally friendly alternative. This review discusses various production methods of bio-PE, including fermentation, gasification, and catalytic conversion of biomass. Interestingly, the bio-PE production volumes and market are expanding due to the growing environmental concerns and regulatory pressures. Additionally, the production of PE and bio-PE biocomposites using agricultural waste as filler materials, highlights the growing demand for sustainable alternatives to conventional plastics. According to previous studies, addition of ≈50% defibrillated corn and abaca fibers into bio-PE matrix and a compatibilizer, results in the highest Young's modulus of 4.61 and 5.81 GPa, respectively. These biocomposites have potential applications in automotive, building construction, and furniture industries. Moreover, the advancement made in abiotic and biotic degradation of PE and PE biocomposites is elucidated to address their environmental impacts. Finally, the paper concludes with insights into the opportunities, challenges, and future perspectives in the sustainable production and utilization of PE and bio-PE biocomposites. In summary, production of PE and bio-PE biocomposites can contribute to a cleaner and sustainable future.

Recyclable, Malleable, and Strong Thermosets Enabled by Knoevenagel Adducts.

Plastic recycling is critical for waste management and achieving a circular economy, but it entails difficult trade-offs between performance and recyclability. Here, we report a thermoset, poly(α-cyanocinnamate) (PCC), synthesized using Knoevenagel condensation between terephthalaldehyde (TPA) and a triarm cyanoacetate star, that tackles this difficulty by harnessing its intrinsically conjugated and dynamic chemical characteristics. PCCs exhibit extraordinary thermal and mechanical properties with a typical Tg of ∼178 °C, Young's modulus of 3.8 GPa, and tensile strength of 102 MPa, along with remarkable flexibility and dimensional and chemical stabilities. Furthermore, end-of-life PCCs can be selectively degraded and partially recycled back into one starting monomer TPA for a new production cycle or reprocessed through dynamic exchange aided by cyanoacetate chain-ends. This study lays the scientific groundwork for the design of robust and recyclable thermosets, with transformative potential in plastic engineering.

Giant Third-Order Nonlinear Hall Effect in Misfit Layer Compound (SnS)1.17(NbS2)3.

The nonlinear Hall effect (NLHE) holds immense significance in recognizing the band geometry and its potential applications in current rectification. Recent discoveries have expanded the study from second-order to third-order nonlinear Hall effect (THE), which is governed by an intrinsic band geometric quantity called the Berry Connection Polarizability tensor. Here we demonstrate a giant THE in a misfit layer compound, (SnS)1.17(NbS2)3. While the THE is prohibited in individual NbS2 and SnS due to the constraints imposed by the crystal symmetry and their band structures, a remarkable THE emerges when a superlattice is formed by introducing a monolayer of SnS. The angular-dependent THE and its scaling relationship indicate that the phenomenon could be correlated to the band geometry modulation, concurrently with the symmetry breaking. The resulting strength of THE is orders of magnitude higher compared to recent studies. Our work illuminates the modulation of structural and electronic geometries for novel quantum phenomena through interface engineering.

Electrically Conductive Polymers for Additive Manufacturing.

The use of electrically conductive polymers (CPs) in the development of electronic devices has attracted significant interest due to their unique intrinsic properties, which result from the synergistic combination of physicochemical properties in conventional polymers with the electronic properties of metals or semiconductors. Most conventional methods adopted for the fabrication of devices with nonplanar morphologies are still challenged by the poor ionic/electronic mobility of end products. Additive manufacturing (AM) brings about exciting prospects to the realm of CPs by enabling greater design freedom, more elaborate structures, quicker prototyping, relatively low cost, and more environmentally friendly electronic device creation. A growing variety of AM technologies are becoming available for three-dimensional (3D) printing of conductive devices, i.e., vat photopolymerization (VP), material extrusion (ME), powder bed fusion (PBF), material jetting (MJ), and lamination object manufacturing (LOM). In this review, we provide an overview of the recent research progress in the area of CPs developed for AM, which advances the design and development of future electronic devices. We consider different AM techniques, vis-à-vis, their development progress and respective challenges in printing CPs. We also discuss the material requirements and notable advances in 3D printing of CPs, as well as their potential electronic applications including wearable electronics, sensors, energy storage and conversion devices, etc. This review concludes with an outlook on AM of CPs.