Abundant Reactive Oxygen Species Research Articles

Cascade loop of ferroptosis induction and immunotherapy based on metal‐phenolic networks for combined therapy of colorectal cancer

AbstractCancer immunotherapy is the most promising method for tumor therapy, while ferroptosis could activate the immunogenicity of cancer and strengthen the cellular immune response. However, limited by the complex tumor microenvironment, the abundant glutathione (GSH) and low reactive oxygen species (ROS) seriously weaken ferroptosis and the immune response. Herein, the authors report photothermal metal‐phenolic networks (MPNs) supplied with buthionine sulfoximine (BSO) by reducing levels of GSH and then trapping the tumor cells in the ferroptosis and immunotherapy cascade loop to eliminate colorectal cancer (CRC). The MPNs coated with the model antigen ovalbumin can accumulate at the tumor site, mediate immunogenic cell death (ICD) under NIR irradiation, and initiate tumoricidal immunity. Then the activated CD8+ T cells would release IFN‐γ to inhibit GPX4 and promote the immunogenic ferroptosis induced by Fe3+ and BSO. Finally, the tumor cells at intertumoral and intratumoral levels would be involved in the ferroptosis‐dominated cancer‐immunity circle for CRC eradication, resulting in outstanding therapeutic outcomes in both primary and distant tumor models. Overall, this strategy employs a photothermal nanoplatform to rapidly stimulate ICD and restrain the oxidation defense system, which provides a promising approach to significantly amplify the “cascade loop” of ferroptosis induction and immunotherapy for treatment of CRC.

PAD4 Inhibitor-Functionalized Layered Double Hydroxide Nanosheets for Synergistic Sonodynamic Therapy/Immunotherapy Of Tumor Metastasis.

Sonodynamic therapy (SDT) is demonstrated to trigger the systemic immune response of the organism and facilitate the treatment of metastatic tumors. However, SDT-mediated neutrophil extracellular traps (NETs) formation can promote tumor cell spread, thus weakening the therapeutic effectiveness of metastatic tumors. Herein, the amorphous CoW-layered double hydroxide (a-CoW-LDH) nanosheets are functionalized with a peptidyl arginine deiminase 4 (PAD4) inhibitor, i.e., YW3-56, to construct a multifunctional nanoagent (a-LDH@356) for synergistic SDT/immunotherapy. Specifically, a-CoW-LDH nanosheets can act as a sonosensitizer to generate abundant reactive oxygen species (ROS) under US irradiation. After loading with YW3-56, a-LDH@356 plus US irradiation not only effectively induces ROS generation and immunogenic cell death, but also inhibits the elevation of citrullinated histone H3 (H3cit) and the release of NETs, enabling a synergistic enhancement of anti-tumor metastasis effect. Using 4T1 tumor model, it is demonstrated that combining a-CoW-LDH with YW3-56 stimulates an anti-tumor response by upregulating the proportion of immune-activated cells and inducing polarization of M1 macrophages, and inhibits immune escape by downregulating the expression of PD-1 on immune cells under US irradiation, which not only arrests primary tumor progression with a tumor inhibition rate of 69.5% but also prevents tumor metastasis with the least number of lung metastatic nodules.

Spatially Axial Boron Coordinated Single‐Atom Nanozymes with Boosted Multi‐Enzymatic Performances for Periodontitis Treatment

AbstractSingle‐atom nanozymes (SAzymes) have made significant strides in antibacterial treatment but fall short as natural enzyme and drug replacements due to limited catalytic performance. Here, a rational strategy is presented for incorporating spatially axial boron (B) ligands to effectively modulate the local coordination environment of planar Fe─N4 motifs (Fe─B/N─C SAzymes). With electronic modulation, the Fe─B/N─C SAzymes exhibit significantly enhanced oxidase‐, peroxidase‐, and catalase‐like activities. Theoretical calculations highlight that the spatially axial B ligands effectively adjust the charge distribution around the planar Fe─N4 active center, which facilitates the heterolysis of H2O2 and the desorption of O2, resulting in accelerated H2O2 decomposition. Furthermore, the intrinsic photothermal effect of Fe─B/N─C SAzymes enhances multienzyme‐like activities, rapidly generating abundant reactive oxygen species (ROS), and achieving chemodynamic/photothermal synergistic therapy for impressive disinfection against periodontal‐related pathogenic bacteria. These findings offer a distinctive viewpoint for optimizing the local coordination environment of SAzymes with axial ligand to enhance their catalytic performance and effectiveness in periodontitis therapy.

Modeling of the particle fluxes of a helium plasma jet onto water surface

The interaction between an atmospheric pressure plasma jet (APPJ) and an aqueous solution has great application prospects in biomedicine and many other fields. Reactive species adjacent to a water surface is critical to the activation of APPJ-treated water, which is affected by both the water evaporation and the admixture of ambient air. In this paper, taking He APPJ as an example, a two-dimensional (2D) cylindrically symmetric fluid model is developed to obtain the spatial distributions of gas components before discharging, and a series of global models are developed for the discharge in the boundary gas layer adjacent to the water surface. The interfacial distributions of reactive species and their fluxes onto the water surface are quantified. It is found that the electron density is 1016–1017 m−3 and it shows an annular distribution in the boundary gas layer. The density distributions of most reactive species there reveal ring-like shapes as well. The dominant cation and anion in such a boundary layer are H3O+ and OH−, respectively. The most abundant metastable is O2(a1Δ), the most abundant reactive oxygen species are H2O2 and OH, and the most abundant reactive nitrogen species are NO and HNO2. The species of H2O2, OH, HO2, and HNO2 are reportedly to have significant biological effects, and in our simulation, their fluxes onto the water surface are remarkable, higher than 1017 m−2 s−1. In addition, the effects of radial gas velocity and water evaporation on the particle flux distributions are also revealed.

Enhanced Fenton performance of wet-mechanochemically synthesized FeS2/Biochar: The multiple synergistic effect derived from mutual element doping

FeS2-biochar composites have been considered as promising heterogeneous Fenton materials for pollutants removal. However, the chemical synthesis of element-doped FeS2-biochar composite with superior performance and the comprehensive investigation for its underlying multiple synergistic mechanism remain a difficult endeavor. Herein, a novel FeS2/Biochar nanocomposite with mutual element doping was firstly synthesized by facile wet-mechanochemical method using iron, sulfur and bamboo-biochar for efficient organic pollutant (sulfamonomethoxine, SMM) removal. Experiment and DFT calculation results revealed that multiple synergistic effect between FeS2 and biochar derived from newly formed Fe-C and C-S-C bonds induced the abundant reactive oxygen species (ROS) and excellent electron transfer capacity. Fe-C sites facilitated the H2O2 adsorption and populated O-O bond in H2O2 for its barrierless dissociation into •OH via forming bridging C-Fe-O-O-Fe bond. Oxygen vacancy, C-S-C and Fe-C bonds, persistent free radicals (PFRs) accelerated the generation and transformation of ROS, which resulted in dominating free radical (•OH, •O2–, •SO4-) and auxiliary non-radical (1O2) pathway. Meanwhile, Fe3+/Fe2+ redox-cycle was expedited by electron donor/shuttle (S22-, BC, •O2–, C-S-C and Fe-C bonds). All these specialties contributed to the superior performance of FeS2/Biochar Fenton system for SMM removal at wide pH range (3–11) with negligible Fe release. Completely SMM (50 mg/L) removal was achieved within 20 min for 8 successive reuses. This work emphasized the concept of building mutual element doping on molecular level in enhancing FeS2-Biochar synergy towards efficient environmental remediation.

Anatase TiO2/Defective UiO-66 porous octahedral S-scheme heterojunctions toward optimized photocatalytic performance

Photocatalysis is an alternative for antibiotics removal from wastewater for the sustainable development of human society. However, applying photocatalysts for antibiotics (e.g., tetracycline) degradation under practical conditions is highly restricted by the low reaction efficiency due to the prompt charge recombination. Constructing porous heterojunctions is an efficient way to regulate the electron transfer path and accelerate charge migration efficiency. Herein, TiO2/defective UiO-66 porous octahedral S-scheme heterojunctions are successfully fabricated through an in-situ growth strategy. The strong interaction and charge migration behavior between TiO2 and defective UiO-66 have been studied using X-ray photoelectron spectroscopy and electron paramagnetic resonance measurements. The photocatalytic removal efficiency of tetracycline is notably improved by forming TiO2/defective UiO-66 porous heterojunctions. The promoted photocatalytic performance can be ascribed to the strong interaction between TiO2 and defective UiO-66, and the accelerated charge separation and transfer efficiency due to the formation of S-scheme heterojunctions, thus generating abundant reactive oxygen species, including O2− and OH. The optimized 38-TiO2/UiO-66-300 can eliminate 97.9 % of tetracycline in 60 min with a reaction constant rate of 0.0425 min−1, which is approximately 4 and 10 times that of pristine TiO2 and UiO-66-300, respectively. This work provides an alternate strategy for preparing highly active heterojunction photocatalysts for environmental applications.

Boosting catalytic oxidation of propane over CeO2-supported Co3O4 catalyst with strong interfacial interaction and electron transfer

Tuning the nanoparticle-support interaction can optimize the catalytic performance of supported metal oxide catalysts for VOCs removal. Herein, a series of Co3O4/CeO2 catalysts with different strengths of interfacial interaction and electron transfer were successfully constructed via various modified wetness impregnation procedures. With the introduction of ammonium hydroxide, citric acid or H2 pretreatment, a stronger interfacial interaction and electron transfer were achieved due to the highly Co3O4 dispersion and CeO2 surface reconstruction. The modified-synthesis Co3O4/CeO2 catalysts, particularly Co3O4/CeO2-CA (citric acid), demonstrated superior catalytic activity (T90 = 296 °C, TOF = 0.337 × 10−3 s−1) and stability for propane oxidation as compared to typical wetness impregnation Co3O4/CeO2-DI (T90 = 314 °C, TOF = 0.121 × 10−3 s−1). Through systematic characterizations and DFT calculation, the strong interfacial interaction and abundant reactive oxygen species facilitate the adsorption and activation of C3H8 and O2 on the catalyst surface, which further promote the intermediates (carbonate/carboxyl species) transformation. These findings highlight interfacial mechanism to catalytic performance optimization of supported metal oxides.

Bimetallic biochar-MOFs composites catalyzing peroxydisulfate in sulfadiazine removal

Sunflower seed husk is a common oil crop by-product. In this study, the husk was used as a base material for preparing a new catalyst, referred to as Fe-Cu-biochar-MOFs. The new material was characterized by multiple nanoscale metal clusters with rough surfaces and irregular shapes, thus providing abundant reactive surface area and sites. The catalytic reactivity was tested using sulfadiazine (SDZ) through batch kinetic experiments, where Fe-Cu-biochar-MOFs were used to activate peroxydisulfate (PDS). The results indicate that the system was able to degrade 95.9% of SDZ within 60 minutes. Mechanistic investigations revealed that the presence of PDS converted Fe0 to Fe2+ and Cu0 to Cu+ in the Fe-Cu-biochar-MOFs, and the resulting Fe(Ⅱ) and Cu(I) ions facilitated the activation of PDS, resulting in abundant reactive oxygen species (1O2, SO4∙− and ∙OH). This work provides a new approach of using waste agricultural by-products for the removal of environmental pollutants.

Photocatalytic degradation of ammonia to nitrogen by anatase TiO2 under microwave discharge electrodeless lamp irradiation

In this study, a microwave discharge electrodeless lamp (MDEL) photo-degradation system coupled with anatase TiO2 (P25) was constructed to improve the selective degradation of NH3 to N2. The MDEL system can generate abundant reactive oxygen species (ROS) with ultraviolet radiation at 185 nm and 254 nm during gas phase reaction. The species and content of ROS generated in the reaction system were determined by oxidation extraction spectrophotometry, and the effects of residence time, temperature, and relative humidity on the production of reactive oxygen species were investigated. In addition, the removal efficiency under different conditions such as initial ammonia concentration, relative humidity and residence time was explored. It was found that the removal rate could reach 83% when the initial ammonia concentration was 100 ppm, relative humidity was 55% and gas residence time was 5.16 s. The high-energy ultraviolet at 185 nm from MDEL could break NH3 molecules in advance and produced a large amount of ·NH2. Besides, NH3 was converted to N2 by generating large amounts of ROS, reducing NOx and nitrate generation. Our work presents a novel approach to construct a photocatalytic system for high efficiency degradation of NH3.

A self-assembled theranostic nanoplatform for efficient tumor sonodynamic-gas therapy

The powerful antioxidant system in tumor tissues limits the efficacy of sonodynamic therapy (SDT) by reducing the availability of the produced reactive oxygen species (ROS). To address this problem, a pH/ultrasound (US) responsive theranostic nanoplatform is elaborately constructed by self-assembly of nitrogen-doped graphene quantum dots (NGQDs), benzothiazole sulfinate (BTS), Gd3+ ions and poly(lactide-co-glycolide)-b-poly(ethylene glycol) (PLGA-PEG). The NGQD component with excellent sonodynamic activity wrapped in the resulting Gd-NGQDs/BTS@PLGA-PEG can efficaciously respond to ultrasonic irradiation and cause abundant ROS generation. Importantly, in response to acidic tumor microenvironment, the loaded BTS sustainably releases SO2, which induces the increase of intracellular •O2− level by inhibiting superoxide dismutase activity and further promotes the enrichment of ROS by reducing intracellular glutathione level and suppressing glutathione peroxidase 4 activity. The well-designed SO2 gas therapy-enhanced SDT strategy leads to high oxidative stress in tumor cells and effective inhibition of the growth of bilateral tumors with only a single intravenous injection of the nanomedicine and a subsequent single US irradiation. Gd-NGQDs/BTS@PLGA-PEG can also be employed as a good T1-weighted magnetic resonance imaging contrast agent to guide tumor therapy. This innovative therapeutic strategy developed in our contribution may provide a new paradigm for the exploration of deep tumor therapy.

Novel Spatially Asymmetric Copper Bismuthate-Mediated Augmentation of Energy Conversion to Realize "Three-Step" Tumor Suppression.

The generally undesirable bandgap and electron-hole complexation of inorganic sonosensitizers limit the efficiency of reactive oxygen species (ROS) generation, affecting the effectiveness of sonodynamic therapy (SDT). Comparatively, the novel polyvinylpyrrolidone-modified copper bismuthate (PCBO) sonosensitizers are manufactured for a "three-step" SDT promotion. In brief, first, the strong hybridization between Bi 6s and O 2p orbitals in PCBO narrows the bandgap (1.83eV), facilitating the rapid transfer of charge carriers. Additionally, nonequivalent [CuO4]6- layers reduce crystal symmetry, confer PCBO unique piezoelectricity, and improve electron-hole separation under ultrasonic (US) excitation. This allows PCBO to convert US energy into chemical energy to produce ROS, achieving the accumulation of abundant ROS, resulting in apoptosis and tumor suppression. Concurrently, PCBO also acts as a glutathione scavenger to reduce tumor antioxidant capacity and improve efficacy. To the best of authors understanding, this study reveals PCBO as an innovative piezoelectric sonosensitizer and provides a meaningful paradigm for designing energy conversion strategies for tumor suppression.

Improving anaerobic digestion sludge properties via heterogeneous activation of peroxydisulfate by CuMgAl-layered double hydroxide

Improving anaerobic digestion sludge (ADS) properties by conditioning technology is necessary for subsequent treatment and disposal. In this study, CuMgAl-layered double hydroxide (CuMgAl-LDH) was prepared by co-precipitation method and applied to activate peroxydisulfate (PDS) for ADS conditioning. Experimental results indicated that under the optimal treatment condition (0.15 g LDH/g TS and 0.2 g PDS/g TS addition), the water content of sludge cake and the time to filter decreased from initial 90.83 % to 82.91 % and 75 min to 39.5 min, respectively, and ortho-P as well as non-biodegradable organics contents in the AD liquor (ADL) also decreased remarkably, which was beneficial for ADS dewatering and subsequent ADL backflow treatment. CuMgAl-LDH activating PDS could produce abundant reactive oxygen species (ROS), resulting in microbial cell disruption, bound water release, sludge particle size decrease and non-biodegradable organics degradation. Mechanisms investigation based on the X-ray photoelectron spectroscopy, electron paramagnetic resonance and ROS quenching experiments results indicated that Cu(I)/Cu(II) redox cycle was responsible for PDS activation, and SO4−· made primary contribution to sludge flocs and cells disruption. This research provided preliminary guideline to design copper-based LDH/PDS system for ADS conditioning in wastewater treatment plants.

Construction of atom co-sharing Bi/Bi4O5Br2 nanosheet heterojunction for plasmonic-enhanced visible-light-driven photocatalytic antibacterial activity

The rapid advancement of photodynamic therapy (PDT) antibacterial materials has led to promising alternatives to antibiotics for treating bacterial infections. However, antibacterial drugs have poor light absorption and utilization rates, which limits their practical application. Constructing two-dimensional (2D) heterojunctions from materials with matching photophysical properties has emerged as a highly effective strategy for achieving high-efficiency photo-antibacterial performance. Here, we designed and prepared an atom co-sharing Bi/Bi4O5Br2 nanosheet heterojunction by a simple in situ reduction. This heterojunction material combines outstanding biocompatibility with excellent bactericidal efficiency, which exceeded 90 % against Escherichia coli (a Gram-negative bacterium) and Staphylococcus aureus (a Gram-positive bacterium) under visible light irradiation, around nine-fold higher than that with pure Bi4O5Br2 nanosheets. The results suggest that localized surface plasmon resonance (LSPR) of shared Bi atoms on the Bi4O5Br2 nanosheets promotes light utilization and the separation and transfer of photo-generated charges, thus producing more abundant reactive oxygen species (ROS), which can partake in the PDT antibacterial effect. Our study underscores the potential utility of LSPR-enhanced Bi-based nanosheet heterojunctions for safe and efficient PDT to combat bacterial infections.

Membrane-anchoring clickable Iridium(III) nanosonosensitizer in situ evokes PANoptosis for augmented tumor sono-immunotherapy

Developing activatable “off-on” sonosensitizers with superior sonodynamic activity and immunogenic cell death (ICD) induction ability is urgently needed for precise and boosted tumor sono-immunotherapy. Herein, a membrane-anchoring clickable Iridium(III) nanosonosensitizer is well-designed to elicit tumor-specific PANoptosis for enhanced sonodynamic therapy (SDT) and amplified immune activation. A click-activatable tetrazine-functionalized Iridium(III) sonosensitizer Tz-Ir with dual type I/II reactive oxygen species (ROS) generation ability is developed, and further encapsulated into crosslinked human serum albumin (HSA) to form acid-responsive nanosonosensitizer HSA@Tz-Ir. After tumor-targeting accumulation and acidic tumor microenvironment (TME)-triggered release, Tz-Ir can synchronously realize efficient click-activation and precise membrane-localization via specific bioorthogonal metabolic glycoengineering technology. Upon US irradiation, in situ activated Tz-Ir can generate abundant ROS to destroy tumor cell membrane for a high-efficiency SDT. Moreover, for the first time, the maximized membrane damage is certified to evoke highly immunogenic PANoptosis (pyroptosis, apoptosis and necroptosis) of tumor cells, resulting in remarkably amplified tumor immunogenicity. The PANoptosis-boosted ICD effect can elicit robust systemic adaptive and innate antitumor immunity to effectively inhibit the growths of primary/distant tumors and lung metastasis. This tumor-specific membrane-targeting SDT modality based on bioorthogonal click activation presents an innovative strategy for precise and augmented tumor sono-immunotherapy.

Enhanced photodynamic inactivation against Escherichia coli O157:H7 provided by chitosan/curcumin coating and its application in food contact surfaces

Sterilisation technologies are essential to eliminate foodborne pathogens from food contact surfaces. However, most of the current sterilisation methods involve high energy and chemical consumption. In this study, a photodynamic inactivation coating featuring excellent antibacterial activity was prepared by dispersing curcumin as a plant-based photosensitiser in a chitosan solution. The coating generated abundant reactive oxygen species (ROS) after light irradiation at 420 nm, which eradicated ≥99.999 % of Escherichia coli O157:H7. It was also found that ROS damaged the cell membrane, leading to the leakage of cell contents and cell shrinkage on the basis of chitosan. In addition, the production of ROS first excited the bacterial antioxidant defence system resulting in the increase of peroxidase (POD) and superoxide dismutase (SOD). ROS levels exceed its capacity, causing damage to the defence system and further oxidative decomposition of large molecules, such as DNA and proteins, eventually leading to the death of E. coli O157:H7. We also found the curcumin/chitosan coating could effectively remove E. coli O157:H7 biofilms by oxidative of extracellular polysaccharides and proteins. All the contributors made the chitosan/curcumin coating an efficient detergent comparable with HClO.

Reactive Oxygen Species Amplifier for Apoptosis-Ferroptosis Mediated High-Efficiency Radiosensitization of Tumors.

Insufficient reactive oxygen species (ROS) production and radioresistance have consistently contributed to the failure of radiotherapy (RT). The development of a biomaterial capable of activating ROS-induced apoptosis and ferroptosis is a potential strategy to enhance RT sensitivity. To achieve precision and high-efficiency RT, the theranostic nanoplatform Au/Cu nanodots (Au/CuNDs) were designed for dual-mode imaging, amplifying ROS generation, and inducing apoptosis-ferroptosis to sensitize RT. A large amount of ROS is derived from three aspects: (1) When exposed to ionizing radiation, Au/CuNDs effectively absorb photons and emit various electrons, which can interact with water to produce ROS. (2) Au/CuNDs act as a catalase-like to produce abundant ROS through Fenton reaction with hydrogen peroxide overexpressed of tumor cells. (3) Au/CuNDs deplete overexpressed glutathione, which causes the accumulation of ROS. Large amounts of ROS and ionizing radiation further lead to apoptosis by increasing DNA damage, and ferroptosis by enhancing lipid peroxidation, significantly improving the therapeutic efficiency of RT. Furthermore, Au/CuNDs serve as an excellent nanoprobe for high-resolution near-infrared fluorescence imaging and computed tomography of tumors. The promising dual-mode imaging performance shows their potential application in clinical cancer detection and imaging-guided precision RT, minimizing damage to adjacent normal tissues during RT. In summary, our developed theranostic nanoplatform integrates dual-mode imaging and sensitizes RT via ROS-activated apoptosis-ferroptosis, offering a promising prospect for clinical cancer diagnosis and treatment.

A pH-sensitive imidazole grafted polymeric micelles nanoplatform based on ROS amplification for ferroptosis-enhanced chemodynamic therapy

Highly toxic reactive oxygen species (ROS), crucial in inducing apoptosis and ferroptosis, are pivotal for cell death pathways in cancer therapy. However, the effectiveness of ROS-related tumor therapy is impeded by the limited intracellular ROS and substrates, coupled with the presence of abundant ROS scavengers like glutathione (GSH). In this research, we developed acid-responsive, iron-coordinated polymer nanoparticles (PPA/TF) encapsulating a mitochondrial-targeting drug alpha-tocopheryl succinate (α-TOS) for enhanced synergistic tumor treatment. The imidazole grafted micelles exhibit prolonged blood circulation and improve the delivery efficiency of the hydrophobic drug α-TOS. Additionally, PPA's design aids in delivering Fe3+, supplying ample iron ions for chemodynamic therapy (CDT) and ferroptosis through the attachment of imidazole groups to Fe3+. In the tumor's weakly acidic intracellular environment, PPA/TF facilitates pH-responsive drug release. α-TOS specifically targets mitochondria, generating ROS and replenishing those depleted by the Fenton reaction. Moreover, the presence of Fe3+ in PPA/TF amplifies ROS upregulation, promotes GSH depletion, and induces oxidative damage and ferroptosis, effectively inhibiting tumor growth. This research presents an innovative ROS-triggered amplification platform that optimizes CDT and ferroptosis for effective cancer treatment.

Electrostatic Field in Contact‐Electro‐Catalysis Driven C−F Bond Cleavage of Perfluoroalkyl Substances

AbstractPerfluoroalkyl substances (PFASs) are persistent and toxic to human health. It is demanding for high‐efficient and green technologies to remove PFASs from water. In this study, a novel PFAS treatment technology was developed, utilizing polytetrafluoroethylene (PTFE) particles (1–5 μm) as the catalyst and a low frequency ultrasound (US, 40 kHz, 0.3 W/cm2) for activation. Remarkably, this system can induce near‐complete defluorination for different structured PFASs. The underlying mechanism relies on contact electrification between PTFE and water, which induces cumulative electrons on PTFE surface, and creates a high surface voltage (tens of volts). Such high surface voltage can generate abundant reactive oxygen species (ROS, i.e., O2⋅−, HO⋅, etc.) and a strong interfacial electrostatic field (IEF of 109~1010 V/m). Consequently, the strong IEF significantly activates PFAS molecules and reduces the energy barrier of O2⋅− nucleophilic reaction. Simultaneously, the co‐existence of surface electrons (PTFE*(e−)) and HO⋅ enables synergetic reduction and oxidation of PFAS and its intermediates, leading to enhanced and thorough defluorination. The US/PTFE method shows compelling advantages of low energy consumption, zero chemical input, and few harmful intermediates. It offers a new and promising solution for effectively treating the PFAS‐contaminated drinking water.

Electrostatic Field in Contact-Electro-Catalysis Driven C-F Bond Cleavage of Perfluoroalkyl Substances.

Perfluoroalkyl substances (PFASs) are persistent and toxic to human health. It is demanding for high-efficient and green technologies to remove PFASs from water. In this study, a novel PFAS treatment technology was developed, utilizing polytetrafluoroethylene (PTFE) particles (1-5 μm) as the catalyst and a low frequency ultrasound (US, 40 kHz, 0.3 W/cm2) for activation. Remarkably, this system can induce near-complete defluorination for different structured PFASs. The underlying mechanism relies on contact electrification between PTFE and water, which induces cumulative electrons on PTFE surface, and creates a high surface voltage (tens of volts). Such high surface voltage can generate abundant reactive oxygen species (ROS, i.e., O2⋅-, HO⋅, etc.) and a strong interfacial electrostatic field (IEF of 109~1010 V/m). Consequently, the strong IEF significantly activates PFAS molecules and reduces the energy barrier of O2⋅- nucleophilic reaction. Simultaneously, the co-existence of surface electrons (PTFE*(e-)) and HO⋅ enables synergetic reduction and oxidation of PFAS and its intermediates, leading to enhanced and thorough defluorination. The US/PTFE method shows compelling advantages of low energy consumption, zero chemical input, and few harmful intermediates. It offers a new and promising solution for effectively treating the PFAS-contaminated drinking water.

Cucumber‐Derived Extracellular Vesicle‐Functionalized Metal‐Organic Frameworks for Enhanced Photodynamic Therapy of Hypertrophic Scars

AbstractPhotodynamic therapy (PDT) with noninvasiveness and high safety has emerged as a promising therapeutic approach for the management of hypertrophic scars (HS). However, the low transdermal delivery and overexpressed levels of intracellular glutathione (GSH) severely hinder its therapeutic effectiveness. Herein, a multifunctional biomimetic nanoplatform (NDs@EV‐RGD) composed of arginine‐glycine‐aspartic acid (RGD)‐modified cucumber‐derived extracellular vesicles (EVs) and copper‐based metal‐organic framework nanodots (Cu‐MOF NDs) is designed for PDT‐mediated HS treatment. The EVs with low Young's modulus exhibit excellent deformability which endow NDs@EV‐RGD with the capacity to overcome the compact stratum corneum barrier, thereby significantly improving their transdermal delivery efficiency. Notably, the RGD targeting peptide displays specific binding to α1β1 integrin on the fibroblast membranes within HS, leading to the high accumulation efficiency of NDs@EV‐RGD at the HS site. Under near‐infrared laser irradiation, NDs@EV‐RGD efficiently generates abundant reactive oxygen species, inducing the apoptosis of excessively proliferated fibroblasts. Moreover, Cu‐MOF NDs interact with the local GSH, leading to GSH depletion and a significant enhancement in PDT efficacy. Furthermore, NDs@EV‐RGD demonstrates a remarkable therapeutic effect in improving the appearance of HS in a rabbit ear HS model, promoting the apoptosis and remodeling of collagen fibers. Therefore, this work provides a promising biomimetic platform for HS treatment.