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.

Engineering High Voltage Aqueous Aluminum-Ion Batteries.

The energy transition to renewables necessitates innovative storage solutions beyond the capacities of lithium-ion batteries. Aluminum-ion batteries (AIBs), particularly their aqueous variants (AAIBs), have emerged as potential successors due to their abundant resources, electrochemical advantages, and eco-friendliness. However, they grapple with achieving their theoretical voltage potential, often yielding less than expected. This perspective article provides a comprehensive examination of the voltage challenges faced by AAIBs, attributing gaps to factors such as the aluminum reduction potential, hydrogen evolution reaction, and aluminum's inherent passivation. Through a critical exploration of methodologies, strategies, such as underpotential deposition, alloying, interface enhancements, tailored electrolyte compositions, and advanced cathode design, are proposed. This piece seeks to guide researchers in harnessing the full potential of AAIBs in the global energy storage landscape.

Hydrolytic degradation and biodegradation of polylactic acid electrospun fibers.

Increased use of bioplastics, such as polylactic acid (PLA), helps in reducing greenhouse gas emissions, decreases energy consumption and lowers pollution, but its degradation efficiency has much room for improvement. The degradation rate of electrospun PLA fibers of varying diameters ranging from 0.15 to 1.33 µm is measured during hydrolytic degradation under different pH from 5.5 to 10, and during aerobic biodegradation in seawater supplemented with activated sewage sludge. In hydrolytic conditions, varying PLA fiber diameter had significant influence over percentage weight loss (W%L), where faster degradation was achieved for PLA fibers with smaller diameter. W%L was greatest for PLA-5 > PLA-12 > PLA-16 > PLA-20, with average W%L at 30.7%, 27.8%, 17.2% and 14.3% respectively. While different pH environment does not have a significant influence on PLA degradation, with W%L only slightly higher for basic environments. Similarly biodegradation displayed faster degradation for small diameter fibers with PLA-5 attaining the highest degree of biodegradation at 22.8% after 90 days. Hydrolytic degradation resulted in no significant structural change, while biodegradation resulted in significant hydroxyl end capping products on the PLA surface. Scanning electron microscopy (SEM) imaging of degraded PLA fibers showed a deteriorated morphology of PLA-5 and PLA-12 fibers with increased adhesion structures and irregularly shaped fibers, while a largely unmodified morphology for PLA-16 and PLA-20.

Next-Generation Vitrimers Design through Theoretical Understanding and Computational Simulations.

Vitrimers are an innovative class of polymers that boast a remarkable fusion of mechanical and dynamic features, complemented by the added benefit of end-of-life recyclability. This extraordinary blend of properties makes them highly attractive for a variety of applications, such as the automotive sector, soft robotics, and the aerospace industry. At their core, vitrimer materials consist of crosslinked covalent networks that have the ability to dynamically reorganize in response to external factors, including temperature changes, pressure variations, or shifts in pH levels. In this review, the aim is to delve into the latest advancements in the theoretical understanding and computational design of vitrimers. The review begins by offering an overview of the fundamental principles that underlie the behavior of these materials, encompassing their structures, dynamic behavior, and reaction mechanisms. Subsequently, recent progress in the computational design of vitrimers is explored, with a focus on the employment of molecular dynamics (MD)/Monte Carlo (MC) simulations and density functional theory (DFT) calculations. Last, the existing challenges and prospective directions for this field are critically analyzed, emphasizing the necessity for additional theoretical and computational advancements, coupled with experimental validation.

Injectable Supramolecular Hydrogels for In Situ Programming of Car-T Cells toward Solid Tumor Immunotherapy.

Chimeric antigen receptor (CAR)-T cell immunotherapy is approved in the treatment of hematological malignancies, but remains far from satisfactory in solid tumor treatment due to inadequate intra-tumor CAR-T cell infiltration. Herein, an injectable supramolecular hydrogel system, based on self-assembly between cationic polymer mPEG-PCL-PEI (PPP) conjugated with T cell targeting anti-CD3e f(ab')2 fragment and α-cyclodextrin (α-CD), is designed to load plasmid CAR (pCAR) with a T cell specific CD2 promoter, which successfully achieves in situ fabrication and effective accumulation of CAR-T cells at the tumor site in humanized mice models. More importantly, due to this tumor microenvironment reprogramming, secretion of cellular inflammatory cytokines (interleukin-2 (IL-2), tumor necrosis factor-α (TNF-α), and interferon-γ (IFN-γ)) or tumor killer protein granzyme B is significantly promoted, which reverses the immunosuppressive microenvironment and significantly enhances the intra-tumor CAR-T cells and cytotoxic T cells infiltration. To the best of the current knowledge, this is a pioneer report of using injectable supramolecular hydrogel for in situ reprogramming CAR-T cells, which might be beneficial for solid tumor CAR-T immunotherapy.

Boosting Solid-State Reconversion Reactivity to Mitigate Lithium Trapping for High Initial Coulombic Efficiency.

An initial Coulombic efficiency (ICE) higher than 90% is crucial for industrial lithium-ion batteries, but numerous electrode materials are not standards compliant. Lithium trapping, due to i) incomplete solid-state reaction of Li+ generation and ii) sluggish Li+ diffusion, undermines ICE in high-capacity electrodes (e.g., conversion-type electrodes). Current approaches mitigating lithium trapping emphasize ii) nanoscaling (<50 nm) to minimize Li+ diffusion distance, followed by severe solid electrolyte interphase formation and inferior volumetric energy density. Herein, this work accentuates i) instead, to demonstrate that the lithium trapping can be mitigated by boosting the solid-state reaction reactivity. As a proof-of-concept, ternary LiFeO2 anodes, whose discharged products contain highly reactive vacancy-rich Fe nanoparticles, can alleviate lithium trapping and enable a remarkable average ICE of ≈92.77%, much higher than binary Fe2 O3 anodes (≈75.19%). Synchrotron-based techniques and theoretical simulations reveal that the solid-state reconversion reaction for Li+ generation between Fe and Li2 O can be effectively promoted by the Fe-vacancy-rich local chemical environment. The superior ICE is further demonstrated by assembled pouch cells. This work proposes a novel paradigm of regulating intrinsic solid-state chemistry to ameliorate electrochemical performance and facilitate industrial applications of various advanced electrode materials.

2D/2D Heterojunction of BiOBr/BiOI Nanosheets for In Situ H2 O2 Production and Activation toward Efficient Photocatalytic Wastewater Treatment.

The presence of toxic organic pollutants in aquatic environments poses significant threats to human health and global ecosystems. Photocatalysis that enables in situ production and activation of H2 O2 presents a promising approach for pollutant removal; however, the processes of H2 O2 production and activation potentially compete for active sites and charge carriers on the photocatalyst surface, leading to limited catalytic performance. Herein, a hierarchical 2D/2D heterojunction nanosphere composed of ultrathin BiOBr and BiOI nanosheets (BiOBr/BiOI) is developed by a one-pot microwave-assisted synthesis to achieve in situ H2 O2 production and activation for efficient photocatalytic wastewater treatment. Various experimental and characterization results reveal that the BiOBr/BiOI heterojunction facilitates efficient electron transfer from BiOBr to BiOI, enabling the one-step two-electron O2 reduction for H2 O2 production. Moreover, the ultrathin BiOI provides abundant active sites for H2 O2 adsorption, promoting in situ H2 O2 activation for •O2 - generation. As a result, the BiOBr/BiOI hybrid exhibits excellent activity for pollutant degradation with an apparent rate constant of 0.141 min-1 , which is 3.8 and 47.3 times that of pristine BiOBr and BiOI, respectively. This work expands the range of the materials suitable for in situ H2 O2 production and activation, paving the way toward sustainable environmental remediation using solar energy.

Revamping Triboelectric Output by Deep Trap Construction.

High output performance is critical for building triboelectric nanogenerators (TENGs) for future multifunctional applications. Unfortunately, the high triboelectric charge dissipation rate has a significant negative impact on its electrical output performance. Herein, a new tribolayer is designed through introducing self-assembled molecules with large energy gaps on commercial PET fibric to form carrier deep traps, which improve charge retention while decreasing dissipation rates. The deep trap density of the PET increases by two orders of magnitude, resulting in an 86% reduction in the rate of charge dissipation and a significant increase in the charge density that can be accumulated on tribolayer during physical contact. The key explanation is that increasing the density of deep traps improves the dielectric's ability to store charges, making it more difficult for the triboelectric charges trapped by the tribolayer to escape from the deep traps, lowering the rate of charge dissipation. This TENG has a 1300% increase in output power density as a result of altering the deep trap density, demonstrating a significant improvement. This work describes a simple yet efficient method for building TENGs with ultra-high electrical output and promotes their practical implementation in the sphere of the Internet of Things.

Water-responsive supercontractile polymer films for bioelectronic interfaces.

Connecting different electronic devices is usually straightforward because they have paired, standardized interfaces, in which the shapes and sizes match each other perfectly. Tissue-electronics interfaces, however, cannot be standardized, because tissues are soft1-3 and have arbitrary shapes and sizes4-6. Shape-adaptive wrapping and covering around irregularly sized and shaped objects have been achieved using heat-shrink films because they can contract largely and rapidly when heated7. However, these materials are unsuitable for biological applications because they are usually much harder than tissues and contract at temperatures higher than 90 °C (refs. 8,9). Therefore, it is challenging to prepare stimuli-responsive films with large and rapid contractions for which the stimuli and mechanical properties are compatible with vulnerable tissues and electronic integration processes. Here, inspired by spider silk10-12, we designed water-responsive supercontractile polymer films composed of poly(ethylene oxide) and poly(ethylene glycol)-α-cyclodextrin inclusion complex, which are initially dry, flexible and stable under ambient conditions, contract by more than 50% of their original length within seconds (about 30% per second) after wetting and become soft (about 100 kPa) and stretchable (around 600%) hydrogel thin films thereafter. This supercontraction is attributed to the aligned microporous hierarchical structures of the films, which also facilitate electronic integration. We used this film to fabricate shape-adaptive electrode arrays that simplify the implantation procedure through supercontraction and conformally wrap around nerves, muscles and hearts of different sizes when wetted for in vivo nerve stimulation and electrophysiological signal recording. This study demonstrates that this water-responsive material can play an important part in shaping the next-generation tissue-electronics interfaces as well as broadening the biomedical application of shape-adaptive materials.

Moist heat as a promising method to decontaminate N95 masks: A large scale clinical study comparing four decontamination modalities-moist heat, steam, ultraviolet-C irradiation, and hydrogen peroxide plasma.

BACKGROUND: Early in the COVID-19 pandemic, there was a global shortage of masks. Although mask reprocessing was practiced, no clinical study has assessed systematically the impact of repeated cycles of wear and decontamination on the integrity of N95 filtering facepiece respirators (FFRs). METHODS: We evaluated mask fit assessed by qualitative respirator fit test (QRFT) after each cycle of wear and decontamination, as well as four measures of mask integrity-bacterial filtration efficacy, particle filtration efficacy, differential pressure, and splash resistance through five cycles of wear and decontamination using one of the four modalities (moist heat, steam, ultraviolet-C irradiation, and hydrogen peroxide plasma). RESULTS: A total of 60.6% (hydrogen peroxide plasma) to 77.5% (moist heat) of the FFRs passed five cycles of wear and decontamination, as assessed by the wearers passing QRFT all five times. Moist heat-decontaminated FFRs retained all technical measures of integrity through all five cycles. CONCLUSIONS: This is the first large-scale study to assess systematically the impact (clinically and quantitatively) on N95 FFR integrity of repeated cycles of wearing followed by decontamination. Our results suggest that moist heat is a promising method for decontaminating N95 FFRs. Performing QRFT after every cycle of wear and decontamination ensures wearer safety. Although there is currently no mask shortage, reprocessing may reduce medical waste and improve sustainability.

MOF-Thermogel Composites for Differentiated and Sustained Dual Drug Delivery.

In recent years, multidrug therapy has gained increasing popularity due to the possibility of achieving synergistic drug action and sequential delivery of different medical payloads for enhanced treatment efficacy. While a number of composite material release platforms have been developed, few combine the bottom-up design versatility of metal-organic frameworks (MOFs) to tailor drug release behavior, with the convenience of temperature-responsive hydrogels (or thermogels) in their unique ease of administration and formulation. Yet, despite their potential, MOF-thermogel composites have been largely overlooked for simultaneous multidrug delivery. Herein, we report the first systematic study of common MOFs (UiO-66, MIL-53(Al), MIL-100(Fe), and MOF-808) with different pore sizes, geometries, and hydrophobicities for their ability to achieve simultaneous dual drug release when embedded within PEG-containing thermogel matrices. After establishing that MOFs exert small influences on the rheological properties of the thermogels despite the penetration of polymers into the MOF pores in solution, the release profiles of ibuprofen and caffeine as model hydrophobic and hydrophilic drugs, respectively, from MOF-thermogel composites were investigated. Through these studies, we elucidated the important role of hydrophobic matching between MOF pores and loaded drugs in order for the MOF component to distinctly influence drug release kinetics. These findings enabled us to identify a viable MOF-thermogel composite containing UiO-66 that showed vastly different release kinetics between ibuprofen and caffeine, enabling temporally differentiated yet sustained simultaneous drug release to be achieved. Finally, the MOF-thermogel composites were shown to be noncytotoxic in vitro, paving the way for these underexploited composite materials to find possible clinical applications for multidrug therapy.

Integration of Single-Atom Catalyst with Z-Scheme Heterojunction for Cascade Charge Transfer Enabling Highly Efficient Piezo-Photocatalysis.

Piezo-assisted photocatalysis (namely, piezo-photocatalysis), which utilizes mechanical energy to modulate spatial and energy distribution of photogenerated charge carriers, presents a promising strategy for molecule activation and reactive oxygen species (ROS) generation toward applications such as environmental remediation. However, similarly to photocatalysis, piezo-photocatalysis also suffers from inferior charge separation and utilization efficiency. Herein, a Z-scheme heterojunction composed of single Ag atoms-anchored polymeric carbon nitride (Ag-PCN) and SnO2- x is developed for efficient charge carrier transfer/separation both within the catalyst and between the catalyst and surface oxygen molecules (O2 ). As revealed by charge dynamics analysis and theoretical simulations, the synergy between the single Ag atoms and the Z-scheme heterojunction initiates a cascade electron transfer from SnO2- x to Ag-PCN and then to O2 adsorbed on Ag. With ultrasound irradiation, the polarization field generated within the piezoelectric hybrid further accelerates charge transfer and regulates the O2 activation pathway. As a result, the Ag-PCN/SnO2- x catalyst efficiently activates O2 into ·O2 - , ·OH, and H2 O2 under co-excitation of visible light and ultrasound, which are consequently utilized to trigger aerobic degradation of refractory antibiotic pollutants. This work provides a promising strategy to maneuver charge transfer dynamics for efficient piezo-photocatalysis by integrating single-atom catalysts (SACs) with Z-scheme heterojunction.

Recent advances in stimuli-responsive polymeric carriers for controllable CRISPR/Cas9 gene editing system delivery.

Non-viral polymeric vectors with good biocompatibility have been recently explored as delivery systems for clustered regularly interspaced short palindromic repeat (CRISPR)-associated (Cas) nucleases. In this review, based on current limitations and critical barriers, we summarize the advantages of stimulus-responsive polymeric delivery vectors (i.e., pH, redox, or enzymes) towards controllable CRISPR/Cas9 genome editing system delivery as well as the advances in using stimulus-responsive CRISPR/Cas9 polymeric carriers towards cancer treatment. Last but not least, the key challenges and promising development strategies of stimulus-responsive polymeric vector designs for CRISPR/Cas9 systems will also be discussed.

Recent Progress in Polyethylene-enhanced Organic Phase Change Composite Materials for Energy Management.

Phase Change Materials (PCMs) are utilized to regulate temperature and store thermal energy in various industries such as infrastructure, electronics, solar power, and more. However, they face several limitations, such as leakage, poor thermal properties, incompatibility, as well as high flammability. Polyethylene (PE) is one of many polymers explored to enhance the desirable properties of PCMs, due to their versatile properties such as high strength, durability, chemical resistance, and low cost. The combination of PCMs and PE can be used to create composite materials, through micro/nano- encapsulation, melt-blending, formation of composites and with proper additives. They create enhanced thermal energy storage properties and in the meantime, benefited from the mechanical properties of the PE. This review provides a concise summary of the recent developments regarding PE-enhanced PCMs and provides insights into possible topics for further investigation. We summarised enhancement methods based on commonly adopted types of PEs, such as encapsulation, melt-blending, hot pressing, extrusion, and 3D printing. We then elaborate on how these PE-PCM composites are effectively utilised for heat management applications and the potential future directions in energy-saving buildings, electronic devices, and energy storage systems.

Battery-free and AI-enabled multiplexed sensor patches for wound monitoring.

Wound healing is a dynamic process with multiple phases. Rapid profiling and quantitative characterization of inflammation and infection remain challenging. We report a paper-like battery-free in situ AI-enabled multiplexed (PETAL) sensor for holistic wound assessment by leveraging deep learning algorithms. This sensor consists of a wax-printed paper panel with five colorimetric sensors for temperature, pH, trimethylamine, uric acid, and moisture. Sensor images captured by a mobile phone were analyzed by neural network-based machine learning algorithms to determine healing status. For ex situ detection via exudates collected from rat perturbed wounds and burn wounds, the PETAL sensor can classify healing versus nonhealing status with an accuracy as high as 97%. With the sensor patches attached on rat burn wound models, in situ monitoring of wound progression or severity is demonstrated. This PETAL sensor allows early warning of adverse events, which could trigger immediate clinical intervention to facilitate wound care management.

Two-Dimensional Layered Materials Meet Perovskite Oxides: A Combination for High-Performance Electronic Devices.

As the Si-based transistors scale down to atomic dimensions, the basic principle of current electronics, which heavily relies on the tunable charge degree of freedom, faces increasing challenges to meet the future requirements of speed, switching energy, heat dissipation, and packing density as well as functionalities. Heterogeneous integration, where dissimilar layers of materials and functionalities are unrestrictedly stacked at an atomic scale, is appealing for next-generation electronics, such as multifunctional, neuromorphic, spintronic, and ultralow-power devices, because it unlocks technologically useful interfaces of distinct functionalities. Recently, the combination of functional perovskite oxides and two-dimensional layered materials (2DLMs) led to unexpected functionalities and enhanced device performance. In this paper, we review the recent progress of the heterogeneous integration of perovskite oxides and 2DLMs from the perspectives of fabrication and interfacial properties, electronic applications, and challenges as well as outlooks. In particular, we focus on three types of attractive applications, namely field-effect transistors, memory, and neuromorphic electronics. The van der Waals integration approach is extendible to other oxides and 2DLMs, leading to almost unlimited combinations of oxides and 2DLMs and contributing to future high-performance electronic and spintronic devices.