Peroxide Ions Research Articles

A Complex Oxide Containing Inherent Peroxide Ions for Catalyzing Oxygen Evolution Reactions in Acid.

Proton exchange membrane water electrolyzers powered by sustainable energy represent a cutting-edge technology for renewable hydrogen generation, while slow anodic oxygen evolution reaction (OER) kinetics still remains a formidable obstacle that necessitates basic comprehension for facilitating electrocatalysts' design. Here, we report a low-iridium complex oxide La1.2Sr2.7IrO7.33 with a unique hexagonal structure consisting of isolated Ir(V)O6 octahedra and true peroxide O22- groups as a highly active and stable OER electrocatalyst under acidic conditions. Remarkably, La1.2Sr2.7IrO7.33, containing 59 wt % less iridium relative to the benchmark IrO2, shows about an order of magnitude higher mass activity, 6-folds higher intrinsic activity than the latter, and also surpasses the state-of-the-art Ir-based oxides ever reported. Combined electrochemical, spectroscopic, and density functional theory investigations reveal that La1.2Sr2.7IrO7.33 follows the peroxide-ion participation mechanism under the OER condition, where the inherent peroxide ions with accessible nonbonded oxygen states are responsible for the high OER activity. This discovery offers an innovative strategy for designing advanced catalysts for various catalytic applications.

Analysis of an open-air argon plasma driven photo-Fenton reaction for degradation of synthetic dyes: Optical emission spectroscopy and statistical design optimization

This research was designed to treat synthetic dyes in aqueous solutions using an atmospheric pressure argon plasma-driven photo-Fenton process. Optical emission spectroscopy and statistical optimization of the argon plasma-driven photo-Fenton process parameters were performed to efficiently degrade synthetic dyes. Lab-scale experiments were performed utilizing an argon plasma jet coupled with a Fenton reagent mixture of hydrogen peroxide (H2O2) and ferrous ions (Fe2+). Based on the response surface methodology, a statistical Box–Behnken design (BBD) was used to optimize the photo-Fenton process by changing Fe2+ concentration, H2O2 concentration, and plasma treatment time as the control factors. Optical emission spectroscopy was conducted to understand the reactive plasma species in the jet. Boltzmann plot was used to study the plasma temperature. The argon plasma jet contained OH, Ar, N2, and atomic oxygen (O) reactive species and radiations in the visible and ultraviolet range. According to BBD, the maximum dye removal efficiency of 97.01% was possible with 40 mg/l of Fe2+ ions, 200 mg/l of H2O2, and 17.5 min of plasma exposure. The statistical model is well-fitted to a second-order polynomial equation. The optimum conditions for dye degradation were Fe2+ (40 g/l), H2O2 (200 g/l), and a plasma treatment time 23.18 min obtained from the optimizer plot. The statistical model showed a 99.76% fit to the experimental data of dye degradation.

Degradation of Amoxicillin in Water by Fenton, Photo-fenton and Photocatalysis Using Copper Oxide

In recent years, the presence of drug residues in water has become a major environmental issue. Among these pollutants is amoxicillin. Our aim is to propose effective methods for decontaminating wastewater containing amoxicillin. This study was carried out using the chemical oxygen demand method. This work has shown that hydroxyl radicals can effectively degrade amoxicillin. The rate of hydroxyl radical production from hydrogen peroxide and iron (II) ions increases in the presence of sunlight. Amoxicillin oxidation is optimal at a pH of 3 and a [H2O2]/[Fe2+] ratio of 13.33. Amoxicillin degradation is faster at low concentrations than at high concentrations. The oxidation of amoxicillin by photo-Fenton results in degradation rates of up to 99%. A study of the adsorption of amoxicillin on copper oxides showed that amoxicillin adsorbs weakly to the amoxicillin surface, with an adsorption rate of 17%. However, in the presence of amoxicillin, hydrogen peroxide and sunlight, degradation rates of up to 99% were obtained. This work has shown that the degradation of amoxicillin is better with solar photo Fenton and solar photocatalysis in the presence of copper oxide than with the Fenton process.

The Metallothionein System in Tetrahymena thermophila Is Iron-Inducible.

Metallothioneins are multifunctional proteins implicated in various cellular processes. They have been used as biomarkers of heavy metal exposure and contamination due to their intrinsic ability to bind heavy metals and their transcriptional response to both physiological and noxious metal ions such as cadmium (Cd) and mercury (Hg). In this study, we aimed to clarify the role of iron and reactive oxygen species (ROSs) in the induction of the metallothionein system (Mtt) in the ciliate protozoan Tetrahymena thermophila. We investigated the relative mRNA abundances of the metallothionein genes Mtt1, Mtt2/4, and Mtt5, revealing for the first time their responsiveness to iron exposure. Furthermore, by using inhibitors of superoxide dismutase (SOD) and catalase (CAT), alone or in combination with iron, we highlighted the roles of superoxide ion and endogenous hydrogen peroxide, as well as the complex interplay between the metal and ROSs. These results enhance our understanding of the metallothionein system in ciliates and suggest that ROSs may be a primary evolutionary driver for the selection of these proteins in nature.

NIR-Actuated Ferroptosis Nanomotor for Enhanced Tumor Penetration and Therapy.

Ferroptosis nano-inducers have drawn considerable attention in the treatment of malignant tumors. However, low intratumoral hydrogen peroxide level and complex biological barriers hinder the ability of nanomedicines to generate sufficient reactive oxygen species (ROS) and achieve tumor penetration. Here a near-infrared (NIR)-driven ROS self-supplying nanomotor is successfully designed for synergistic tumor chemodynamic therapy (CDT) and photothermal therapy (PTT). Janus nanomotor is created by the asymmetrical modification of polydopamine (PDA) with zinc peroxide (ZnO2) and subsequent ferrous ion (Fe2+) chelation via the polyphenol groups from the PDA, here refer as ZnO2@PDA-Fe (Z@P-F). ZnO2 is capable of slowly releasing hydrogen peroxide (H2O2) into an acidic tumor microenvironment (TME) providing sufficient ingredients for the Fenton reaction necessary for ferroptosis. Upon NIR laser irradiation, the loaded Fe2+ is released and a thermal gradient is simultaneously formed owing to the asymmetric PDA coating, thus endowing the nanomotor with self-thermophoresis based enhanced diffusion for subsequent lysosomal escape and tumor penetration. Therefore, the release of ferrous ions (Fe2+), self-supplied H2O2, and self-thermophoresis of nanomotors with NIR actuation further improve the synergistic CDT/PTT efficacy, showing great potential for active tumor therapy.

Curative effect of hydrogen peroxide combined with silver ion disinfection on pelvic floor dysfunction.

Pelvic floor dysfunction (PFD) is related to muscle fiber tearing during childbirth, negatively impacting postpartum quality of life of parturient. Appropriate and effective intervention is necessary to promote PFD recovery. To analyze the use of hydrogen peroxide and silver ion disinfection for vaginal electrodes in conjunction with comprehensive rehabilitation therapy for postpartum women with PFD. A total of 59 women with PFD who were admitted to the hospital from May 2019 to July 2022 were divided into two groups: Control group (n = 27) received comprehensive rehabilitation therapy and observation group (n = 32) received intervention with pelvic floor biostimulation feedback instrument in addition to comprehensive rehabilitation therapy. The vaginal electrodes were disinfected with hydrogen peroxide and silver ion before treatment. Intervention for both groups was started 6 weeks postpartum, and rehabilitation lasted for 3 months. Pelvic floor muscle voltage, pelvic floor muscle strength, vaginal muscle voltage, vaginal muscle tone, pelvic floor function, quality of life, and incidence of postpartum PFD were compared between the two groups. Before comprehensive rehabilitation treatment, basic data and pelvic floor function were not significantly different between the two groups. After treatment, the observation group showed significant improvements in the maximum voltage and average voltage of pelvic floor muscles, contraction time of type I and type II fibers, pelvic floor muscle strength, vaginal muscle tone, vaginal muscle voltage, and quality of life (GQOLI-74 reports), compared with the control group. The observation group had lower scores on the pelvic floor distress inventory (PFDI-20) and a lower incidence of postpartum PFD, indicating the effectiveness of the pelvic floor biostimulation feedback instrument in promoting the recovery of maternal pelvic floor function. The combination of the pelvic floor biostimulation feedback instrument and comprehensive rehabilitation nursing can improve pelvic floor muscle strength, promote the recovery of vaginal muscle tone, and improve pelvic floor function and quality of life. The use of hydrogen peroxide and silver ion disinfectant demonstrated favorable antibacterial efficacy and is worthy of clinical application.

A novel edible coating based on Albizia [Albizia lebbeck (L.) Benth.] gum delays softening and maintains quality of harvested guava fruits during storage

Guava, a commercially important fruit crop, is being grown in tropical and subtropical regions around the world. Due to the perishable nature of guava fruits, there are great losses during marketing, transport and storage. The application of edible coating is emerging as a low-cost, simple to implement and efficient method for extending the postharvest life of fresh horticultural produces, such as fruits and vegetables. This study aimed to assess the potential of Albizia gum (AZG) to improve storability and maintain the overall fruit quality of stored guava fruits. Freshly harvested guava fruits were coated with 0 % (control), 1.5 %, 3 % or 4.5 % AZG. After coating treatment, the fruits were stored at 20 ± 1 °C and 85–90 % relative humidity for 15 days. The results revealed that 4.5% AZG coating suppressed the weight loss and decay incidence up to 27 % and 36 %, respectively, as compared with control. The fruits coated with 4.5 % AZG had the maximum titratable acidity (0.40 %), ascorbic acid (104.47 mg·100 g−1), total antioxidants (118.84 mmol Trolox·100 g−1), total phenolics (285.57 mg·kg−1) and flavonoids (60.12 g·kg−1) on 15th day of storage. However, the minimum total soluble solids (11.97 %), sugar-acid ratio (29.31), relative ion leakage (68.40 %), malondialdehyde (0.11 nmol·kg−1 FW) and hydrogen peroxide (16.05 μmol·kg−1 FW) were recorded in the fruits of same treatment on 15th day of storage. Furthermore, the activities of antioxidant enzymes “i.e., superoxide dismutase (SOD), peroxidase (POD), catalase (CAT), and ascorbate peroxidase (APX)” were increased under the influence of AZG coating. Consequently, as compared to uncoated fruits, AZG-coated fruits exhibited reduced activities of fruit softening enzymes “i.e., cellulase, pectin methylesterase (PME), and polygalacturonase (PG)”. To sum up, the application of AZG-based edible coating could markedly improve the storage life of guavas and maintain overall fruit quality.

Turmeric-Black Cumin Essential Oils and Their Capacity to Attenuate Free Radicals, Protein Denaturation, and Cancer Proliferation.

Turmeric rhizomes (Curcuma longa) and black cumin seeds (Nigella sativa) are polyherbal ingredients used for the management of cancer and other chronic inflammatory diseases in Nigerian ethnomedicine. Previous studies have shown the antioxidant, anti-inflammatory, and anticancer activities of the individual plant extracts. However, the two spices have not been biologically potentiated in their combined form. Therefore, this study obtained essential oils (EOs) from the combined spices and evaluated their inhibitory effects on free radicals, protein denaturation, and cancer proliferation. The EOs were extracted by hydro-distillation (HD) and characterized by gas chromatography-mass spectrometry (GC-MS). In vitro antioxidant assessment was conducted based on DPPH, hydrogen peroxide (H2O2), nitric oxide (NO), and ferric ion (Fe3+) radical scavenging assays. The cytotoxicity of the oil against non-tumorigenic (HEK293) and cancerous (HepG2 and HeLa) cell lines was determined following the MTT cell viability assay. An in silico molecular docking analysis of the oil constituents was also performed. Six batches of EOs I-VI were afforded, comprising twenty-two major constituents, with aromatic Ar-turmerone being the most prominent compound. There was a marked improvement in the bioactivity of the oils upon repeated HD and as a combination. The batch VI oil exhibited the best activity, with a cytotoxicity (CC50) of 10.16 ± 1.69 µg/100 µL against the HepG2 cell line, which was comparable to 5-fluorouracil (standard, CC50 = 8.59 ± 1.33 µg/100 µL). In silico molecular docking suggested δ-curcumene, Ar-curcumene, Ar-turmerol, and Ar-turmerone among the promising compounds based on their high binding energy scores with NOX2, NF-κB, and mdm2 proteins. In conclusion, the oils from the turmeric-black cumin combined possess a considerable inhibition ability against free radicals, protein denaturation, and cancer proliferation. This study's findings further underscore the effectiveness of turmeric-black cumin as a polyherbal medicinal ingredient.

Nitrogen-based redox couple regulated anionic redox to long-term cycling stability of Li and Mn-rich layered oxide cathode for Li-ion batteries

Lithium and manganese-rich layered oxides (LMROs) have attracted extensive attention and are promising cathode materials for next-generation lithium ion batteries due to their high capacities and high energy densities. However, LMRO cathode suffers from severe capacity and voltage fading originating from irreversible surface oxygen evolution. Herein, we propose a facile redox couple strategy by introducing nitroxyl radicals species to regulate the surface anionic redox reaction of LMRO cathode. Differential electrochemical mass spectroscopy, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy analyses demonstrate that during charge process, the peroxide ion O22− on the surface generated from the oxidation of lattice O2− could be reduced back to stable O2− by redox couple in time, thus avoiding oxygen evolution and structure degradation, as well as enhancing bulk oxygen redox activity. The enhanced LMRO electrode delivers a high capacity of 220.3 mAh g−1 at 1 C. An excellent cycling stability with a capacity retention of 94.4 % is achieved after 500 cycles, as well as a suppressed voltage decay with only 1.12 mV per cycle.

Viscosity reduction of xanthan gum through free radical mechanisms mediated by ascorbic acid

Xanthan gum (XG) is a widely used thickener known for its high viscosity and excellent stability. However, the presence of ascorbic acid (AA) leads to a clear decrease in its viscosity, thereby affecting the application of xanthan gum in food products containing AA. Therefore, the aim of this study was to uncover the mechanism by which AA reduces the viscosity of xanthan gum. Ascorbic acid (0.1 mmol/L) caused a viscosity loss reaching up to 96% for xanthan gum solutions (2 g/L). The reaction was further enhanced by heating at 60 °C for 1 h without stirring, a weakly acidic system at pH 5.4, and the addition of hydrogen peroxide or metal ions (Fe2+ and Cu2+). Interestingly, AA induction produces free radicals and changes in their content correlate with a decrease in XG viscosity. Moreover, removing dissolved oxygen by heating and nitrogen purging treatment effectively reduced AA-derived free radical levels and prevented the decrease in XG viscosity. The decrease in viscosity of XG caused by AA involved its free radicals generated through an oxygen-dependent pathway.

Cu-N Synergism Regulation to Enhance Anionic Redox Reversibility and Activity of Li- and Mn-Rich Layered Oxides Cathode.

Anionic redox chemistry enables extraordinary capacity for Li- and Mn-rich layered oxides (LMROs) cathodes. Unfortunately, irreversible surface oxygen evolution evokes the pernicious phase transition, structural deterioration, and severe electrode-electrolyte interface side reaction with element dissolution, resulting in fast capacity and voltage fading of LMROs during cycling and hindering its commercialization. Herein, a redox couple strategy is proposed by utilizing copper phthalocyanine (CuPc) to address the irreversibility of anionic redox. The Cu-N synergistic effect of CuPc could not only inhibit surface oxygen evolution by reducing the peroxide ion O2 2- back to lattice oxygen O2-, but also enhance the reaction activity and reversibility of anionic redox in bulk to achieve a higher capacity and cycling stability. Moreover, the CuPc strategy suppresses the interface side reaction and induces the forming of a uniform and robust LiF-rich cathode electrolyte, interphase (CEI) to significantly eliminate transition metal dissolution. As a result, the CuPc-enhanced LMRO cathode shows superb cycling performance with a capacity retention of 95.0% after 500 long-term cycles. This study sheds light on the great effect of N-based redox couple to regulate anionic redox behavior and promote the development of high energy density and high stability LMROs cathode.

Cadmium induced defense enhance the invasive potential of Wedelia trilobata under herbivore infestation

Cadmium (Cd) pollution is on the rise due to rapid urbanization, which emphasize the potential adverse effects on plant biodiversity and human health. Wedelia as a dominant invasive species, is tested for its tolerance to Cd-toxicity and herbivore infestation. We investigate defense mechanism system of invasive Wedelia trilobata and its native congener Wedelia chinensis against the Cd-pollution and Spodoptera litura infestation. We found that Cd-toxicity significantly increase hydrogen peroxide (H2O2), Malondialdehyde (MDA) and hydroxyl ions (O2•) in W. chinensis 20.61%, 4.78% and 15.68% in leave and 27.44%, 25.52% and 30.88% in root, respectively. The photosynthetic pigments (Chla, Chla and Caro) and chlorophyll florescence (Fo and Fv/Fm) declined by (60.23%, 58.48% and 51.96%), and (73.29% and 55.75%) respectively in W. chinensis and (44.76%, 44.24% and 44.30%), and (54.66% and 45.36%) in W. trilobata under Cd treatment and S. litura. Invasive W. trilobata had higher enzymatic antioxidant SOD 126.9/71.64%, POD 97.24/94.92%, CAT 53.99/25.62% and APX 82.79/50.19%, and nonenzymatic antioxidant ASA 10.47/16.87%, DHA 15.07/27.88%, GSH 15.91/10.03% and GSSG 13.56/17.93% activity in leaf/root, respectively. Overall, W. trilobata accumulate higher Cd content 55.41%, 50.61% and 13.95% in root, shoot and leaf tissues respectively, than its native congener W. chinensis. While, nutrient profile of W. chinensis reveals less uptake of Fe, Cu and Zn than W. trilobata. W. trilobata showed efficient alleviation of oxidative damage through upregulating the genes related to key defense such as SOD, POD, CAT, APX, GR, PROL, FLV, ABA and JAZ, and metal transporter in leaves, shoot and root tissues, respectively. Conclusively, W. trilobata efficiently employed Cd-triggered defense for successful invasion, even under S. litura infestation, in Cd-contaminated soil.

Ultrasound Effect on the Hydrogen Peroxide Oxidation of Corn Starch, Molecular Structure, and Functional Properties of Obtained Starch Derivatives

AbstractThis study aims to determine the effect of ultrasound on the oxidation process of starch, molecular structure, and its functional properties. Corn starch is oxidized by hydrogen peroxide (with Cu(II) or Fe(II) ions as catalysts) in the ultrasound field. Changes in starch structure are identified based on determinations of the carboxyl, carbonyl groups, copper, iron content, molecular characterization by GPC, crystallinity, gelatinization characteristics, and surface area. Functional properties are determined based on analysis of color parameters, water binding capacity, solubility in water, and pasting characteristics. It is found that the effectiveness of the starch oxidation under ultrasound is affected by the presence and type of catalysts. The content of metal incorporated into starch during oxidation is approximately 15% lower when an ultrasound treatment is applied. When starch oxidation is assisted with ultrasound, the metal incorporation preferentially occurs in the pores and holes of the grain. Starches oxidized in the presence of Fe(II) and Cu(II) catalysts can be successfully used not only as thickeners in food industry but also as metal carriers in many industries.

Oxygen Release Suppression and Electronic Conductivity Enhancement for High Performance Li‐ and Mn‐Rich Layered Oxides Cathodes by Chalcogenide Redox Couple and Oxygen Vacancy Generations

AbstractLi‐ and Mn‐rich layered oxides (LMROs) are promising cathode materials for next‐generation lithium‐ion batteries (LIBs) due to their high capacity and high energy density. However, they suffer from severe capacity and voltage fading during cycling, where the irreversible oxygen release during cycle is deemed to a severe factor. Herein, this put forward a general oxygen release suppression strategy by introducing small amounts of sodium chalcogenides during cathode slurry preparation. The formed unstable surface peroxide ions O22− of LMRO during charging is reduced to stable O2− by chalcogen ion and couples the formation of sodium chalcogenic oxides, which is reduced to sodium chalcogenides and O2− during discharging. As a result, the oxygen release is significantly suppressed and the structural stability of LMRO is greatly enhanced. Meanwhile, abundant surface oxygen vacancies are generated coupling with evidently increased carrier concentration and mobility, thus enhancing electronic conductivity significantly. The Li1.2Ni0.13Co0.13Mn0.54O2 cathode with 3 wt% Na2Se shows a capacity retention as high as 96.2% and a capacity of 225 mAh g−1 after 500 cycles at 1 C, coupling with a high capacity of 135 mAh g−1 at 10 C. The relevant mechanism for the improved electrochemical properties is revealed, which is hopefully helpful for novel strategy design to high‐performance LMRO cathodes.

Elevated tropospheric ozone and crop production: potential negative effects and plant defense mechanisms.

Ozone (O3) levels on Earth are increasing because of anthropogenic activities and natural processes. Ozone enters plants through the leaves, leading to the overgeneration of reactive oxygen species (ROS) in the mesophyll and guard cell walls. ROS can damage chloroplast ultrastructure and block photosynthetic electron transport. Ozone can lead to stomatal closure and alter stomatal conductance, thereby hindering carbon dioxide (CO2) fixation. Ozone-induced leaf chlorosis is common. All of these factors lead to a reduction in photosynthesis under O3 stress. Long-term exposure to high concentrations of O3 disrupts plant physiological processes, including water and nutrient uptake, respiration, and translocation of assimilates and metabolites. As a result, plant growth and reproductive performance are negatively affected. Thus, reduction in crop yield and deterioration of crop quality are the greatest effects of O3 stress on plants. Increased rates of hydrogen peroxide accumulation, lipid peroxidation, and ion leakage are the common indicators of oxidative damage in plants exposed to O3 stress. Ozone disrupts the antioxidant defense system of plants by disturbing enzymatic activity and non-enzymatic antioxidant content. Improving photosynthetic pathways, various physiological processes, antioxidant defense, and phytohormone regulation, which can be achieved through various approaches, have been reported as vital strategies for improving O3 stress tolerance in plants. In plants, O3 stress can be mitigated in several ways. However, improvements in crop management practices, CO2 fertilization, using chemical elicitors, nutrient management, and the selection of tolerant crop varieties have been documented to mitigate O3 stress in different plant species. In this review, the responses of O3-exposed plants are summarized, and different mitigation strategies to decrease O3 stress-induced damage and crop losses are discussed. Further research should be conducted to determine methods to mitigate crop loss, enhance plant antioxidant defenses, modify physiological characteristics, and apply protectants.

Copper nitroprusside: An innovative approach for targeted cancer therapy via ROS modulation

The clinical application of nanomaterials for chemodynamic therapy (CDT), which generate multiple reactive oxygen species (ROS), presents significant challenges. These challenges arise due to insufficient levels of endogenous hydrogen peroxide and catalytic ions necessary to initiate Fenton reactions. As a result, sophisticated additional delivery systems are required. In this study, a novel bimetallic copper (II) pentacyanonitrosylferrate (Cu(II)NP, Cu[Fe(CN) 5 NO]) material was developed to address these limitations. This material functions as a multiple ROS generator at tumoral sites by self-inducing hydrogen peroxide and producing peroxynitrite (ONOO-) species. The research findings demonstrate that this material exhibits low toxicity towards normal liver organoids, yet shows potent antitumoral effects on High Grade Serous Ovarian Cancer (HGSOC) organoid patients, regardless of platinum resistance. Significantly, this research introduces a promising therapeutic opportunity by proposing a single system capable of replacing the need for H2O2, additional catalysts, and NO-based delivery systems. This innovative system exhibits remarkable multiple therapeutic mechanisms, paving the way for potential advancements in clinical treatments.

Human serum albumin and sialic acid co-modified liposome nanoreactors with tumor-specific activable cascade reactions for cooperative cancer therapy

Herein, a new type of human serum albumin (HSA) and sialic acid (SA) co-modified liposome nanoreactor was prepared to realize chemotherapy and chemodynamic therapy cooperative treatment of tumor. Firstly, Paclitaxel (PTX) acidic sensitive prodrug with a maleimide-terminated functional group and a sialic acid-modified reduced glutathione (GSH) sensitive paclitaxel prodrug have been synthesized. Then, a liposome nanoreactor was prepared by using PTX prodrugs, lecithin, and cholesterol as membrane materials, and simultaneously encapsulating water-soluble Fe3O4 and glucose oxidase. Finally, HSA was bound to the surface of liposomes through the Michael addition between maleimide-terminated functional group of PTX prodrug and the thiol group at the cysteine 34 residue of human serum albumin. The cumulative release rates of PTX in nanoreactor were 43.98 % at pH = 5.5 and 14.98 % at pH 7.4 after 96h respectively, exhibiting pH sensitive drug release behavior. Also 25.98 % and 17.52 % of PTX release were observed respectively in the medium with 10 mM DTT and without DTT after 96h, displaying redox responsive drug release behavior. The fluorescence intensity of tumor sites for the Dir loaded nanoreactor was higher than that of the free Dir group, displaying the targeting ability of HSA and SA. In tumor site, glucose oxidase can catalyze glucose to generate hydrogen peroxide, and hydroxyl radical is generated under an iron-based Fenton reaction between hydrogen peroxide and iron ion to kill tumor cells to realize chemodynamic therapy. After administration, the average tumor weight of the NS group was 2.516g, while nanoreactor group was 0.322g, displaying the synergistic therapy and excellent anticancer efficacy.

Theoretical exploration of single-molecule magnetic and single-molecule toroic behaviors in peroxide-bridged double-triangular {MII3LnIII3} (M = Ni, Cu and Zn; Ln = Gd, Tb and Dy) complexes.

Detailed state-of-the-art ab initio and density functional theory (DFT) calculations have been undertaken to understand both Single-Molecule Magnetic (SMM) and Single-Molecule Toroic (SMT) behaviors of fascinating 3d-4f {M3Ln3} triangular complexes having the molecular formula [MII3LnIII3(O2)L3(PyCO2)3](OH)2(ClO4)2·8H2O (with M = Zn; Ln = Dy (1), Tb (2) & Gd (3) and M = Cu; Ln = Dy (4), Tb (5) & Gd (6)) and [Ni3Ln3(H2O)3(mpko)9(O2)(NO3)3](ClO4)·3CH3OH·3CH3CN (Ln = Dy (7), Tb (8), and Gd (9)) [mpkoH = 1-(pyrazin-2-yl)ethanone oxime]. All these complexes possess a peroxide ligand that bridges the {LnIII3} triangle in a μ3-η3:η3 fashion and the oxygen atoms/oxime of co-ligands that connect each MII ion to the {LnIII3} triangle. Through our computational studies, we tried to find the key role of the peroxide bridge and how it affects the SMM and SMT behavior of these complexes. Primarily, ab initio Complete Active Space Self-Consistent Field (CASSCF) SINGLE_ANISO + RASSI-SO + POLY_ANISO calculations were performed on 1, 2, 4, 5, 7, and 8 to study the anisotropic behavior of each Ln(III) ion, to derive the magnetic relaxation mechanism and to calculate the LnIII-LnIII and CuII/NiII-LnIII magnetic coupling constants. DFT calculations were also performed to validate these exchange interactions (J) by computing the GdIII-GdIII and CuII/NiII-GdIII interactions in 3, 6, and 9. Our calculations explained the experimental magnetic relaxation processes and the magnetic exchange interactions for all the complexes, which also strongly imply that the peroxide bridge plays a role in the SMM behavior observed in these systems. On the other hand, this peroxide bridge does not support the SMT behavior. To investigate the effect of bridging ions in {M3Ln3} systems, we modeled a {ZnII3DyIII3} complex (1a) with a hydroxide ion replacing the bridged peroxide ion in complex 1 and considered a hydroxide-bridged {CoIII3DyIII3} complex (10) having the formula [Co3Dy3(OH)4(OOCCMe3)6(teaH)3(H2O)3](NO3)2·H2O. We discovered that as compared to the LoProp charges of the peroxide ion, the greater negative charges on the bridging hydroxide ion reduce quantum tunneling of magnetization (QTM) effects, enabling more desirable SMM characteristics and also leading to good SMT behavior.

Sprayable oxidized polyvinyl alcohol with improved degradability and sufficient mechanical property for fruit preservation.

Besides their limited preservation capacity and low biosafety, traditional fruit preservation procedures exacerbate "white pollution" because they utilize excessive plastic. Herein, an environmentally friendly one-pot method was developed to obtain degradable polyvinyl alcohol (PVA), where the hydroxyl radicals generated through the reaction between hydrogen peroxide (H2O2) and iron ions functioned to oxidize PVA. The oxidized PVA (OPVA-1.0) with abundant ketone groups, reduced crystallinity, and short molecular chains was completely degraded into H2O and CO2 after being buried in the soil for ∼60 days. An improvement in its degradation rate did not weaken the mechanical properties of OPVA-1.0 compared to other modified PVA films because the adverse effect of decreased crystallinity on its mechanical performance was offset by its ion coordination. Alternatively, the tensile strength or toughness of OPVA-1.0 was enhanced due to its internal multi-level interactions including molecular chain entanglement, hydrogen bonding, and metal coordination bonds. More interestingly, OPVA-1.0 was water-welded into various products in a recyclable way owing to its reversible physical bonds, where it was sprayed, dipped, or brushed conformally onto different perishable fruits to delay their ripening by 5-14 days. Based on the cellular biocompatibility and biosafety evaluations in mice, OPVA-1.0 obtained by the facile oxidation strategy was demonstrated to alleviate "white pollution" and delay the ripening of fruits effectively.

Human breast milk-derived phospholipid DOPE ameliorates intestinal injury associated with NEC by inhibiting ferroptosis.

Neonatal necrotizing enterocolitis (NEC) is a severe inflammatory bowel disease that commonly affects premature infants. Breastfeeding has been proven to be one of the most effective methods for preventing NEC. However, the specific role of lipids, the second major nutrient category in human breast milk (HBM), in intestinal development remains unclear. Our preliminary lipidomic analysis of the HBM lipidome revealed that dioleoyl phosphatidylethanolamine (DOPE) is not only abundant but also shows high solubility in lipids, endowing it with significant biological utility. Experimental results confirmed that DOPE significantly reduces the mortality of neonatal rats, ameliorates impairment of intestinal barrier function, and alleviates the expression of intestinal inflammatory factors IL-1β and IL-6. Furthermore, DOPE promotes the migration and proliferation of intestinal epithelial cells, thereby enhancing the integrity of the intestinal barrier function in vitro. The progression of NEC is linked with the onset of ferroptosis. Our cellular-level analysis of lipid peroxide and iron ion concentrations revealed that DOPE significantly reduces the indicators of ferroptosis, while also modulating the expression of pivotal ferroptosis-associated factors, including SLC7A11, GPX4, and ACSL4. Hence, this research on DOPE is expected to provide novel insights into the bioactive lipids present in HBM.