A Mg Battery-Integrated Bioelectronic Patch Provides Efficient Electrochemical Stimulations for Wound Healing.

Bioelectronic patches hold promise for patient-comfort wound healing providing simplified clinical operation. Currently, they face paramount challenges in establishing long-term effective electronic interfaces with targeted cells and tissues due to the inconsistent energy output and high bio interface impedance. Here a new electrochemical stimulation technology is reported, using a simple wound patch, which integrates the efficient generation and delivery of stimulation. This is realized by employing a hydrogel bioelectronic interface as an active component in an integrated power source (i.e., Mg battery). The Mg battery enhances fibroblast functions (proliferation, migration, and growth factor secretion) and regulates macrophage phenotype (promoting regenerative polarization and down-regulating pro-inflammatory cytokines), by providing an electric field and the ability to control the cellular microenvironment through chemical release. This bioelectronic patch shows an effective and accelerated wound closure by guiding epithelial migration, mediating immune response, and promoting vasculogenesis. This new electrochemical-mediated therapy may provide a new avenue for user-friendly wound management as well as a platform for fundamental insights into cell stimulation.

A wearable iontophoresis enables dual-responsive transdermal delivery for atopic dermatitis treatment.

Atopic dermatitis is a chronic, inflammation skin disease that remains a major public health challenge. The current drug-loading hydrogel dressings offer numerous benefits with enhanced loading capacity and a moist-rich environment. However, their development is still limited by the accessibility of a suitable driven source outside the clinical environment for precise control over transdermal delivery kinetics. Here, we prepare a sulfonated poly(3,4-ethylenedioxythiophene) (PEDOT) polyelectrolyte hydrogel drug reservoir that responds to different stimuli-both endogenous cue (body temperature) and exogenous cue (electrical stimulation), for wearable on-demand transdermal delivery with enhanced efficacy. Functioned as both the drug reservoir and cathode in a Zn battery-powered iontophoresis patch, this dual-responsive hydrogel achieves high drug release efficiency (68.4 %) at 37 °C. Evaluation in hairless mouse skin demonstrates the efficacy of this technology by facilitating transdermal transport of 12.2 µg cm-2 dexamethasone phosphate when discharged with a 103 Ω external resistor for 3 h. The Zn battery-driven iontophoresis results in an effective treatment of atopic dermatitis, displaying reductions in epidermal thickness, mast cell infiltration inhibition, and a decrease in IgE levels. This work provides a new treatment modality for chronic epidermal diseases that require precise drug delivery in a non-invasive way.

Reusing the Wasted Energy of Electrochromic Smart Window for Near-Zero Energy Building.

Electrochromic smart windows (ESWs) are an effective energy-saving technology for near-zero energy buildings. They consume electric energy unidirectionally during a round-trip coloring-bleaching process, with the energy involved in the bleaching process being wasted. It is highly desirable to reuse this wasted electric energy directly and/or transfer it into other energy storage equipment, further enhancing the overall efficiency of electric energy usage. Herein, a zinc anode-based ESW (ESW-PZ) is reported that not only has fascinating visible-near-infrared (VIS-NIR) dual-band electrochromic performance (a high optical contrast of 63%) but also showcases good energy storage characteristics (a wide voltage window of 2.6 V and a high energy density of 127.5 µWh cm-2). The buildings utilizing ESW-PZ to modulate indoor environments demonstrated an average annual energy saving of 366 MJ m-2 based on energy simulations, which is about 16% of the total energy consumption. Impressively, a high utilization efficiency of 90% (855 mWh m-2) of the wasted electric energy is realized through an ingenious circuit-switching strategy, which can be reused to power small household appliances.

A Wearable Self-Charging Electroceutical Device for Bacteria-Infected Wound Healing.

The prolonged wound-healing process caused by pathogen infection remains a major public health challenge. The developed electrical antibiotic administration typically requires metal electrodes wired to a continuous power supply, restricting their use beyond clinical environments. To obviate the necessity for antibiotics and an external power source, we have developed a wearable synergistic electroceutical device composed of an air self-charging Zn battery. This battery integrates sustained tissue regeneration and antibacterial modalities while maintaining more than half of the initial capacity after ten cycles of chemical charging. In vitro bacterial/cell coculture with the self-charging battery demonstrates inhibited bacterial activity and enhanced cell function by simulating the endogenous electric field and dynamically engineering the microenvironment with released chemicals. This electroceutical device provides accelerated healing of a bacteria-infected wound by stimulating angiogenesis and modulating inflammation, while effectively inhibiting bacterial growth at the wound site. Considering the simple structure and easy operation for long-term treatment, this self-charging electroceutical device offers great potential for personalized wound care.

Wearable dual-drug controlled release patch for psoriasis treatment.

Wearable drug delivery systems (DDS) have made significant advancements in the field of precision medicine, offering precise regulation of drug dosage, location, and timing. The performance qualities that wearable DDS has always strived for are simplicity, efficiency, and intelligence. This paper proposes a wearable dual-drug synergistic release patch. The patch is powered by a built-in magnesium battery and utilizes a hydrogel containing viologen-based hyperbranched polyamidoamine as both a cathode material and an integrated drug reservoir. This design allows for the simultaneous release of both dexamethasone and tannic acid, overcoming the limitations of monotherapy and ensuring effective synergy for on-demand therapy. In a mouse model with praziquimod-induced psoriasis, the patch demonstrated therapeutic efficacy at a low voltage. The inflammatory skin returned to normal after 5 days with the on-demand release of dual drugs. This work provides a promising treatment option considering its straightforward construction and the therapeutic advantages of dual-drug synergy.

Bifunctional Potential Structure Design Breaks Electrolyte Limitations of Zinc Ion Battery.

Aqueous zinc-ion batteries (ZIBs) are safe and economical for grid applications. However, current ZIBs have limitations in terms of inferior capacity and low output voltage, which are hampered by the electrolyte applicability of the Zn2+ hosts. In this study, we propose a novel organic cathode design strategy with a bifunctional potential region. This polymeric Zn2+ host combines the conjugated polyaniline backbone to tune the molecular surface pH and [Fe(CN)6]3-/4- redox couple for high output voltage and capacity. The polyaniline doped with ferricyanide (PAF) electrode exhibits two forms of charge storage in ZIBs: proton-assisted Zn2+ doping below 1.2 V (mechanism I), and [Fe(CN)6]3-/4- redox pair above 1.8 V (mechanism II). Density functional theory calculations and in situ pH experiments demonstrated that the H+ doping process of mechanism I forms a localized pH regulation on the molecular chain surface, providing a favorable reaction environment for mechanism II. The Zn-polymer battery delivered an outstanding discharge capacity (405.2 mAh g-1) and high output voltage (1.8 V) in the Zn(CF3SO3)2 electrolyte. This study provides a new route for enhancing the structural stability of electrodes and overcoming the electrolyte limitations of ferricyanide in weakly acidic electrolytes.

Conductive Viologen Hydrogel Based on Hyperbranched Polyamidoamine for Multiple Stimulus-Responsive Drug Delivery.

The emergence of precision medicine and personalized pharmacotherapy has led to the development of advanced drug delivery systems that can respond to multiple stimuli. Conductive hydrogels have excellent electrical signal responsiveness and drug storage capabilities; however, current conductive hydrogels suffer from poor mechanical properties, low ionic conductivity, and high voltage. Herein, a covalently crosslinked viologen hydrogel was prepared using electroactive hyperbranched polyamidoamine (EHP) as the crosslinking center in a polymeric network. Attributed to its unique molecular architecture, this hydrogel exhibits improved mechanical properties (high tensile strength and desirable stretchability up to 1280%). Approvable ionic conductivity, biocompatibility, antibacterial properties, and wearable strain-sensing performance were also disclosed, ascribed to the participation of versatile viologen groups in the hydrogel structure. This hydrogel exhibited high efficiency in drug release (81.6%) at a lower voltage of -1.2 V. Moreover, fascinating pH-stimulus drug release behavior was also demonstrated in both acidic and alkalescent environments owing to the dramatic conformational transition of EHP. This work provides a new design strategy for conductive hydrogels for multiple stimulus-responsive drug delivery systems.

Application and Development of Silicon Anode Binders for Lithium-Ion Batteries.

The use of silicon (Si) as a lithium-ion battery's (LIBs) anode active material has been a popular subject of research, due to its high theoretical specific capacity (4200 mAh g-1). However, the volume of Si undergoes a huge expansion (300%) during the charging and discharging process of the battery, resulting in the destruction of the anode's structure and the rapid decay of the battery's energy density, which limits the practical application of Si as the anode active material. Lithium-ion batteries' capacity, lifespan, and safety can be increased through the efficient mitigation of Si volume expansion and the maintenance of the stability of the electrode's structure with the employment of polymer binders. The main degradation mechanism of Si-based anodes and the methods that have been reported to effectively solve the Si volume expansion problem firstly are introduced. Then, the review demonstrates the representative research work on the design and development of new Si-based anode binders to improve the cycling stability of Si-based anode structure from the perspective of binders, and finally concludes by summarizing and outlining the progress of this research direction.

A Piezoelectric-Driven Electrochromic/Electrofluorochromic Dual-Modal Display Device.

Electrochromic (EC) reflective displays offer great advantages in delivering information and providing visual data, but are limited in dark environments. Reflective/emissive dual-modal displays capable of electrochemically-induced color and fluorescence change simultaneously are highly desirable, especially possessing rapid response speed as well as long-term durability. Herein, an electroactive fluorescent ionic liquid based on triphenylamine and imidazole (EFIL-TPA) has been synthesized for reflective/emissive dual-modal display. The resultant device exhibits outstanding electrochromic/electrofluorochromic (EC/EFC) performance with low driving voltage (below 1.0 V), fast switching speed (0.57-1.8 s), and remarkable cycling durability (91% retention for 10 000 cycles). A piezoelectric nanogenerator (PENG) driven EC/EFC integrated system is fabricated to harvest energy from human motion and visually drive the color/fluorescence change for human motion indication in both bright and dark environments. This innovative EC/EFC dual-modal display device based on EFIL-TPA supports a huge space for the development of self-powered human motion visualized indication in all-light conditions.

A biocompatible and fully erodible conducting polymer enables implanted rechargeable Zn batteries.

Implanted rechargeable batteries that can provide energy over a sufficient lifetime and ultimately degrade into non-toxic byproducts are highly desirable. However, their advancement is significantly impeded by the limited toolbox of electrode materials with a known biodegradation profile and high cycling stability. Here we report biocompatible, erodible poly(3,4-ethylenedioxythiophene) (PEDOT) grafted with hydrolyzable carboxylic acid pendants. This molecular arrangement combines the pseudocapacitive charge storage from the conjugated backbones and dissolution via hydrolyzable side chains. It demonstrates complete erosion under aqueous conditions in a pH-dependent manner with a predetermined lifetime. The compact rechargeable Zn battery with a gel electrolyte offers a specific capacity of 31.8 mA h g-1 (57% of theoretical capacity) and outstanding cycling stability (78% capacity retention over 4000 cycles at 0.5 A g-1). Subcutaneous implantation of this Zn battery into Sprague-Dawley (SD) rats demonstrates complete biodegradation in vivo and biocompatibility. This molecular engineering strategy presents a viable avenue for developing implantable conducting polymers with a predetermined degradation profile and high energy storage capability.

An integrated Mg battery-powered iontophoresis patch for efficient and controllable transdermal drug delivery.

Wearable transdermal iontophoresis eliminating the need for external power sources offers advantages for patient-comfort when deploying epidermal diseases treatments. However, current self-powered iontophoresis based on energy harvesters is limited to support efficient therapeutic administration over the long-term operation, owing to the low and inconsistent energy supply. Here we propose a simplified wearable iontophoresis patch with a built-in Mg battery for efficient and controllable transdermal delivery. This system decreases the system complexity and form factors by using viologen-based hydrogels as an integrated drug reservoir and cathode material, eliminating the conventional interface impedance between the electrode and drug reservoir. The redox-active polyelectrolyte hydrogel offers a high energy density of 3.57 mWh cm-2, and an optimal bioelectronic interface with ultra-soft nature and low tissue-interface impedance. The delivery dosage can be readily manipulated by tuning the viologen hydrogel and the iontophoresis stimulation mode. This iontophoresis patch demonstrates an effective treatment of an imiquimod-induced psoriasis mouse. Considering the advantages of being a reliable and efficient energy supply, simplified configuration, and optimal electrical skin-device interface, this battery-powered iontophoresis may provide a new non-invasive treatment for chronic epidermal diseases.

Interface Reversible Electric Field Regulated by Amphoteric Charged Protein-Based Coating Toward High-Rate and Robust Zn Anode.

Metallic interface engineering is a promising strategy to stabilize Zn anode via promoting Zn2+ uniform deposition. However, strong interactions between the coating and Zn2+ and sluggish transport of Zn2+ lead to high anodic polarization. Here, we present a bio-inspired silk fibroin (SF) coating with amphoteric charges to construct an interface reversible electric field, which manipulates the transfer kinetics of Zn2+ and reduces anodic polarization. The alternating positively and negatively charged surface as a build-in driving force can expedite and homogenize Zn2+ flux via the interplay between the charged coating and adsorbed ions, endowing the Zn-SF anode with low polarization voltage and stable plating/stripping. Experimental analyses with theoretical calculations suggest that SF can facilitate the desolvation of [Zn(H2O)6]2+ and provide nucleation sites for uniform deposition. Consequently, the Zn-SF anode delivers a high-rate performance with low voltage polarization (83 mV at 20 mA cm-2) and excellent stability (1500 h at 1 mA cm-2; 500 h at 10 mA cm-2), realizing exceptional cumulative capacity of 2.5 Ah cm-2. The full cell coupled with ZnxV2O5·nH2O (ZnVO) cathode achieves specific energy of ~ 270.5/150.6 Wh kg-1 (at 0.5/10 A g-1) with ~ 99.8% Coulombic efficiency and retains ~ 80.3% (at 5.0 A g-1) after 3000 cycles.

Preparation and Electrochromic Properties of Benzodithiophene-Isoindigo Conjugated Polymers with Oligoethylene Glycol Side Chains.

Functional polymers featuring good processability in non-halogenated, benzene-free green solvents are highly desired due to health and environmental concerns. Herein, a series of novel D-A type conjugated polymers, PBDT-IIDs, are designed and successfully prepared by "green" functionalization of the polymers with highly hydrophilic, highly polar, highly flexible, and biocompatible oligoethylene glycol (OEG) side chains in order to improve the processability. These series polymers are named PBDT-IID2, PBDT-IID3, and PBDT-IID4, respectively, according to the number of oxygen atoms in the side chain. After confirmation by structural characterization, the basic properties of PBDT-IIDs are also investigated. With the increase in the OEG side chain length, the polymer PBDT-IID4 not only has good solubility in the halogen solvent chlorobenzene, but also exhibits excellent solubility in the green halogen-free solvent methyltetrahydrofuran (Me-THF). As a result, the green solvent Me-THF can also be applied to prepare PBDT-IIDs' electrochromic active layers, except for chlorobenzene and toluene. The electrochromism of PBDT IIDs under both positive and negative voltages has a practical application potential. The several controllable switches between dark green and khaki (0-0.6 V) are expected to show great potential in the field of military camouflage. Furthermore, according to the principle of red, green, and blue (RGB) mixing, light blue-green in the reduced state (-1.6 V) can be used in the preparation of complementary ECDs to provide one of the three primary colors (green).

Bioinspired Catechol-Grafting PEDOT Cathode for an All-Polymer Aqueous Proton Battery with High Voltage and Outstanding Rate Capacity.

Aqueous all-polymer proton batteries (APPBs) consisting of redox-active polymer electrodes are considered safe and clean renewable energy storage sources. However, there remain formidable challenges for APPBs to withstand a high current rate while maximizing high cell output voltage within a narrow electrochemical window of aqueous electrolytes. Here, a capacitive-type polymer cathode material is designed by grafting poly(3,4-ethylenedioxythiophene) (PEDOT) with bioinspired redox-active catechol pendants, which delivers high redox potential (0.60 V vs Ag/AgCl) and remarkable rate capability. The pseudocapacitive-dominated proton storage mechanism illustrated by the density functional theory (DFT) calculation and electrochemical kinetics analysis is favorable for delivering fast charge/discharge rates. Coupled with a diffusion-type anthraquinone-based polymer anode, the APPB offers a high cell voltage of 0.72 V, outstanding rate capability (64.8% capacity retention from 0.5 to 25 A g-1 ), and cycling stability (80% capacity retention over 1000 cycles at 2 A g-1 ), which is superior to the state-of-the-art all-organic proton batteries. This strategy and insight provided by DFT and ex situ characterizations offer a new perspective on the delicate design of polymer electrode patterns for high-performance APPBs.

Multiple Stimuli-Responsive Fluorescence Behavior of Novel Polyamic Acid Bearing Oligoaniline, Triphenylamine, and Fluorene Groups.

Multiple stimuli-responsive fluorescent materials have gained increasing attention for their fundamental investigation and intelligent applications. In this work, we report design and synthesis of a novel polyamic acid bearing oligoaniline, triphenylamine, and fluorene groups, which served as sensitive units and fluorescence emission unit, respectively. The resulting polymer exhibits multiple stimuli-responsive fluorescence switching behavior triggered by redox species, pH, electrochemical, and pressure stimuli. Every fluorescence switching mechanism upon each stimulus was studied in detail. The interactions and energy transfer between sensitive units and emission unit are largely responsible for this fascinating fluorescent switching behavior. This work provides a deep understanding of the optical switching essence upon these stimuli, opening the way for the development of new fluorescent sensing applications.

Electroactive self-doped poly(amic acid) with oligoaniline and sulfonic acid groups: synthesis and electrochemical properties.

A novel poly(amic acid) with pendant aniline tetramer and sulfonic acid groups (ESPAA) was synthesized by ternary polymerization and characterized by Fourier-transform infrared spectra, ((1))H NMR and gel permeation chromatography. The polymer showed good thermal stability and excellent solubility in the common organic solvents. The electrochemical properties were investigated carefully on a CHI 660A Electrochemical Workstation. The polymer displayed good electroactivity in acid, neutral and even in alkaline solutions (pH=1-10) due to the self-doping effect between aniline tetramer and sulfonic/carboxylic acid groups. It also exhibited satisfactory electrochromic performance with high contrast value, acceptable coloration efficiency and fast switching time in the range of pH=1-9.

Intra-chain photodimerization of pendant anthracene units as an efficient route to single-chain nanoparticle fabrication.

An efficient route to architecturally defined, sub-20 nm soft nanoparticles fabricated from single polymer chains via intramolecular photodimerization of pendant anthracene units is presented. Photodimerization is confirmed by the disappearance of the characteristic anthracene π-π* absorption peak at ≈ 360 nm measured by UV-vis spectroscopy. Size exclusion chromatography (SEC) with UV, multi-angle light scattering (MALS), and viscometric detection confirms that as photodimers form, the chains fold to form nanoparticles, demonstrated by shifts in the SEC traces to longer retention times as a function of increased irradiation time. These shifts indicate a reduction in hydrodynamic radius, corroborated and quantified by viscometric data. MALS detector traces reveal the presence of a small amount of chain-chain coupling during this process, but confirm that this is primarily a single-chain phenomenon. Electron microscopy provides visual confirmation of nanoparticle formation.

Tuning the fluorescent response of a novel electroactive polymer with multiple stimuli.

A novel polymer featuring oligoaniline pendants that exhibits reversible electroactivity and good electrochromic properties with high contrast value, acceptable switching times, and excellent coloration efficiency is presented. This polymer can undergo reversible changes in fluorescence in response to reductive and oxidative chemical stimulus, pH, and electrical potential. The fluorescence switching operation shows reasonable reversibility and reproducibility when subjected to multiple stimuli. In this elegant fluorescence switching system, the oligoaniline pendants are used as fluorophore and regulatory units simultaneously.

A facile strategy to decorate Cu9S5 nanocrystals on polyaniline nanowires and their synergetic catalytic properties.

Here, we demonstrated a novel method to decorate Cu9S5 nanocrystals on polyaniline (PANI) nanowires using the dopant of mercaptoacetic acid (MAA) in the PANI matrix as the sulfur source under a hydrothermal reaction. TEM images showed that Cu9S5 nanocrystals with a size in the range of 5-20 nm were uniformly formed on the surface of PANI nanowires. Significantly, the as-prepared PANI/Cu9S5 composite nanowires have been proven to be novel peroxidase mimics toward the oxidation of the peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H2O2. Due to the synergetic effects between polyaniline nanowires and Cu9S5 nanocrystals, the obtained PANI/Cu9S5 composite nanowires exhibit superior catalytic activity over the independent components. This work not only presents a simple and versatile method to decorate semiconductor nanocrystals on the surface of conducting polymer nanostructures, but also provides fundamental guidelines for further investigations into the synergetic effect between conducting polymers and other materials.

Controlled folding of a novel electroactive polyolefin via multiple sequential orthogonal intra-chain interactions.

We report here the synthesis of a novel electroactive polyolefin and demonstrate through a combination of SEC-MALS and DLS how this type of functional polymer can be folded in a controlled fashion from an expanded coil to a tightly wound globule using sequentially activated noncovalent and covalent intra-chain interactions.