Catalytic Peroxide Research Articles

Hollow Copper Sulfide Nanocubes Loaded with Pt(IV) Complexes for Cancer Multimodal Therapy.

Chemotherapy (CT) can significantly inhibit tumor growth, metastasis, and recurrence during cancer therapy. People have widely used platinum drugs in cancer treatment. However, as most chemotherapeutic drugs, platinum drugs still have shortcomings such as poor solubility, low cell uptake, nonspecific distribution, multidrug resistance, and adverse side effects. Therefore, we synthesized hollow copper sulfide (CuS) nanocubes with photothermal and photodynamic properties as carriers for Pt(IV) drugs. Hollow CuS nanocubes have attracted considerable interest in the field of cancer photothermal therapy (PTT) using multiple biological windows. Under near-infrared (NIR) laser irradiation, Cu2+ can be reduced into Cu+ in the presence of hydrogen peroxide in the tumor microenvironment. The resulting Cu+ can be used for photodynamic therapy (PDT), which can perform a Fenton-like reaction under acidic conditions (pH 5.5-6.5) and catalyze hydrogen peroxide to produce ·OH in the tumor microenvironment. In addition, compared with Pt(II) drugs, Pt(IV) drugs not only have lower systemic toxicity but also consume glutathione (GSH), thereby increasing reactive oxygen species (ROS) levels in tumor cells and effectively promoting PDT. In this study, we oxidized ethylenediamine platinum chloride to its tetravalent state, loaded the Pt(IV) complexes using hollow CuS nanocubes, and modified the surfaces of the nanoparticles with PEG to improve the EPR effect. The Pt(IV)-loaded hollow CuS nanocubes modified with PEG (Pt(IV)-CuS@PEG) are expected to be used for tumor chemo/photothermal/photodynamic therapy.

An Intelligent Triple Assisted Gold Cluster‐Based Nanosystem for Enhanced Tumor Photodynamic Therapy

Comprehensive SummaryPhotodynamic therapy (PDT) has been attracted a surge of research interest. However, there are several obstacles to limit the efficacy of PDT, such as hypoxic tumor microenvironment (TME), overexpressed glutathione (GSH), inefficient reactive oxygen species (ROS) generation, and so on. Herein, a smart responsive nanosystem was constructed, which was composed of Au25 modified with triphenylphosphine (Au25‐TPP), catalase (CAT) and GSH‐responsive diselenide‐bridged mesoporous silica nanoparticles (Se‐MSN). When the nanosystem arrived at tumor site, Se‐MSN was degraded by the intracellular overexpressed GSH to release Au25‐TPP and CAT. The Au25‐TPP was targeted to mitochondria and generated ROS under the 808 nm NIR laser irradiation to kill tumor cells. Simultaneously, CAT could catalyze hydrogen peroxide to provide oxygen for relieving the hypoxia of TME. Besides, GSH was consumed by the diselenide bond to diminish the ROS loss. The above tactics (mitochondria targeting, hypoxia relieving and GSH consuming) jointly enhanced the PDT efficacy. The nanosystem showed distinct in vitro anticancer effect significantly stronger than other groups containing one or two assistance. Moreover, the in vivo results suggested that the tumors could be restrained obviously. The current study provides a new inspiration for constructing novel inorganic nanomedicines with multiple enhancement effect of PDT efficacy.

Nanozyme-Shelled Microcapsules for Targeting Biofilm Infections in Confined Spaces.

Bacterial infections in irregular and branched confinements pose significant therapeutic challenges. Despite their high antimicrobial efficacy, enzyme-mimicking nanoparticles (nanozymes) face difficulties in achieving localized catalysis at distant infection sites within confined spaces. Incorporating nanozymes into microrobots enables the delivery of catalytic agents to hard-to-reach areas, but poor nanoparticle dispersibility and distribution during fabrication hinder their catalytic performance. To address these challenges, a nanozyme-shelled microrobotic platform is introduced using magnetic microcapsules with collective and adaptive mobility for automated navigation and localized catalysis within complex confinements. Using double emulsions produced from microfluidics as templates, iron oxide and silica nanoparticles are assembled into 100-µm microcapsules, which self-organize into multi-unit, millimeter-size assemblies under rotating magnetic fields. These microcapsules exhibit high peroxidase-like activity, efficiently catalyzing hydrogen peroxide to generate reactive oxygen species (ROS). Notably, microcapsule assemblies display remarkable collective navigation within arched and branched confinements, reaching the targeted apical regions of the tooth canal with high accuracy. Furthermore, these nanozyme-shelled microrobots perform rapid catalysis in situ and effectively kill biofilms on contact via ROS generation, enabling localized antibiofilm action. This study demonstrates a facile method of integrating nanozymes onto a versatile microrobotic platform to address current needs for targeted therapeutic catalysis in complex and confined microenvironments.

Polyvalent copper oxide nanozymes: Co-delivery of ROS and NO for inducing cuproptosis-like bacterial death against MRSA infections

The development of highly effective and low-toxicity antimicrobials is one of the important challenges for combat methicillin-resistant Staphylococcus aureus (MRSA) infections. Recent studies have found that cuproptosis-like bacterial death is an effective strategy to overcome drug resistance. Here, we designed and synthesized a valence in situ conversion of polyvalent copper oxide nanozymes (L-CuxO NPs), which modified L-arginine (L-Arg) to enhance antibacterial ability. In vitro studies showed that L-CuxO NPs can catalyze hydrogen peroxide (H2O2) to produce hydroxyl radical (•OH), mediate NO release, and continuously consume glutathione (GSH) through change of valence state of Cu2+ and Cu+. Importantly, copper overload in bacteria restricts the tricarboxylic acid (TCA) cycle, promoting bacterial cuproptosis-like death. In vivo results confirmed that L-CuxO NPs is not only effective in alleviating acute MRSA lung infection, but also accelerates the healing of MRSA infected wounds. Accordingly, this study provides a new idea for overcoming bacterial resistance and structural innovation of novel nanozymes.

Piezoelectric-mediated two-dimensional copper-based metal–organic framework for synergistic sonodynamic and cuproptosis-driven tumor therapy

Sonodynamic therapy (SDT) is a minimally invasive therapeutic approach that utilizes sonosensitizers to catalyze substrates and generate reactive oxygen species (ROS) under ultrasound stimulation, ultimately inducing tumor cell death. Enhancing the piezoelectric properties of nanomaterials and modulating the semiconductor energy band are effective strategies to improve the catalytic efficiency of sonosensitizers. In this study, we developed a two-dimensional (2D) copper-based piezoelectric metal–organic framework (MOF) sonosensitizer, denoted as CM, through the coordination of copper and dimethylimidazole. The unique 2D MOF structure imparts CM with piezoelectric characteristics, enabling it to enhance SDT efficacy by modulating the semiconductor bandgap and carrier mobility. Upon ultrasound irradiation, CM catalyzes oxygen to undergo a cascade reaction, producing highly toxic singlet oxygen. Additionally, cupric ions in CM can be reduced by glutathione, facilitating the spontaneous catalysis of hydrogen peroxide in tumors to generate hydroxyl radicals and deplete glutathione, thereby inducing oxidative damage. Moreover, cupric ions in CM can trigger tumor cell cuproptosis, which, in combination with the generated ROS, accelerates cell death. Thus, this study establishes a MOF-based system for controllably inducing multi-pathway cancer cell death and provides a foundation for enhancing ultrasound-catalyzed tumor therapy through the optimization of piezoelectric properties.

Enhancing the Self-Propelled Motion of Hydrogen Peroxide Fueled Active Particles with Formic Acid and Other Oxygen Scavengers.

We report enhanced active particle motion in hydrogen peroxide-fueled self-diffusiophoretic active particle systems of up to 400% via addition of low concentrations of oxygen scavenging agents such as formic acid (as well as other organic acids, hydrazine, and citric acid), whereas active motion was inhibited at higher concentrations. Control experiments showed that enhanced motion was decoupled from catalytic hydrogen peroxide decomposition rate and insensitive to particle surface chemistry. Experimental results point to bulk oxygen scavenging as the cause for the enhanced active motion, representing a realization of recently predicted promotional effects of product sinks on self-diffusiophoretic motion. Diminished active motion at high oxygen scavenger concentrations was attributed to catalytic site blocking by adsorbed solute.

Gelatin-coated glutathione depletion and oxygen generators in potentiated chemotherapy for pancreatic cancer

Chemotherapy is generally acknowledged as an effective method for pancreatic cancer (PC). However, its treatment efficacy is often compromised due to inefficient drug delivery and drug resistance propensity of tumor tissues. The purpose of this study is to design and develop a novel drug delivery system (Manganese-doped mesoporous silica nanoparticles, Mn-MSN) in which paclitaxel (PTX), a conventional chemotherapeutic agent used to effectively treat pancreatic cancer clinically. Through cross-linking with glutaraldehyde, gelatin (Ge) was encapsulated on the carrier surface, endowing the nanoparticles (Ge-Mn-MSN@PTX) with excellent biocompatibility, low hemolytic activity, and enzyme-responsive degradation. Mn was added for the following purposes: (1) catalyzing hydrogen peroxide (H2O2) to generate oxygen (O2), thereby alleviating tumor hypoxia and drug resistance; (2) depleting glutathione (GSH), inducing intracellular lipid peroxidation and ferroptosis; (3) enabling real-time monitoring of the therapeutic efficacy of the nanoparticles via magnetic resonance imaging (MRI). The experimental results demonstrated that Ge-Mn-MSN@PTX has satisfactory biosafety, antitumor activity, controlled drug release as well as imaging tracking capabilities. In the SW1990 nude mice model, the Ge-Mn-MSN@PTX effectively inhibited tumor growth by suppressing the expression of the resistance protein P-glycoprotein (P-gp) and inducing ferroptosis. In conclusion, the designed gelatin-coated Mn-MSN shows potential for application in future pancreatic cancer therapy.

Understanding the Role of Corrosion and Reactive Oxygen Species in Electrochemical Ozone Production on Nickel and Antimony Doped Tin Oxide

Electrochemical ozone production (EOP), a six-electron reaction, offers promising green applications for water disinfection and organic synthesis. Nickel and antimony-doped tin oxide (Ni/Sb-SnO2, NATO) electrodes are known to be active for EOP. Still, the mechanism of NATO's selectivity and activity and the origin of its instability need to be clarified. We combine electrochemistry, spectroscopic detection of reactive oxygen species (ROS) using selective chemical probes, oxygen anion chemical ionization mass spectrometry (CIMS), and density-functional theory (DFT) simulations to identify the reaction mechanism and investigate the role of corrosion and homogenous reactive oxygen species in EOP on NATO electrodes. We identify hydrogen peroxide as a critical reaction intermediate. Our results suggest that the presence of nickel in NATO enables the catalysis of hydrogen peroxide to hydroperoxyl radicals, which subsequently undergo oxidation to produce ozone. The isotopic makeup of products shows that water is the primary source of ozone, but it also contains oxygen from the metal oxide lattice. The change in the isotopic generation pattern of ozone suggests that NATO catalysts corrode irreversibly, and the lattice oxygen is not regenerated, explaining NATO's instability.

Polyoxometalate-based iron-organic complex nanozymes with peroxidase-like activities for colorimetric detection of hydrogen peroxide and ascorbic acid.

As a new type of artificial enzyme, ananozyme is an ideal substitute for natural enzymes and has been successfully applied in many fields. However, in the application of biomolecular detection, most nanozymes have the disadvantages of long reaction times or high detection limits, prompting researchers to search for new efficient nanozymes. In this work, the enzyme-like activities of three polyoxometalate-based iron-organic complexes ([Fe(bpp)2](Mo6O19), [Fe(bpp)2]2(Mo8O26)·2CH3OH, and [Fe(bpp)2]4H[Na(Mo8O26)]3), namely, FeMo6, Fe2Mo8, and Fe4Mo8Na, were analyzed. All three polyoxometalate-based iron-organic complexes were found to be capable of catalyzing hydrogen peroxide (H2O2) to oxidize 3,3',5,5'-tetramethylbenzidine and o-phenylenediamine, resulting in visible color changes, further exhibiting peroxidase-like activity. Results showed that Fe4Mo8Na had more active sites due to its long chain structure, endowing more prominent peroxidase-like activity compared with Fe2Mo8 and FeMo6. A colorimetric sensing platform for H2O2 and ascorbic acid detection based on Fe4Mo8Na was established. The linear response range for H2O2 detection was 0.5-100μM, and the detection limit was 0.143μM. The linear response for ascorbic acid detection ranges from 0 to 750μM with a detection limit of 1.07μM. This study provides a new perspective for developing new nanozymes and expanding the sensing and detection application of nanozymes.

Tumor microenvironment responsive chitosan-coated W-doped MoOx biodegradable composite nanomaterials for photothermal/chemodynamic synergistic therapy

Chemodynamic therapy (CDT), an approach that eradicates tumor cells through the catalysis of hydrogen peroxide (H2O2) into highly toxic hydroxyl radicals (·OH), possesses distinct advantages in tumor specificity and minimal side effects. However, CDT's therapeutic efficacy is currently hampered by the low production efficiency of ·OH. To address this limitation, this study introduces a water-soluble chitosan-coated W-doped MoOx (WMoOx/CS) designed for the combined application of photothermal therapy (PTT) combined with CDT. The W-doped MoOx (WMoOx) was synthesized in one step by the hydrothermal method, and its surface was modified by water-soluble chitosan (carboxylated chitosan, CS) to enhance its biocompatibility. WMoOx boasts a high near-infrared photothermal conversion efficiency of 52.66 %, efficiently transducing near-infrared radiation into heat. Moreover, the Mo4+/Mo5+ and W5+ ions in WMoOx catalyze H2O2 to produce ·OH for CDT, and the Mo5+/Mo6+ and W6+ ions in WMoOx reduce intracellular glutathione levels and prevent the scavenging of ·OH by glutathione. Crucially, the combination of WMoOx/CS and near-infrared light irradiation demonstrates promising synergistic antitumor effects in both in vitro and in vivo models, highlighting its potential for the combined application of PTT and CDT.

Dual-recognition colorimetric platform based on porous Au@Pt nanozymes for highly sensitive washing-free detection of Staphylococcus aureus.

Adual-recognition strategy is reportedto construct a one-step washing and highly efficient signal-transduction tag system for high-sensitivity colorimetric detection of Staphylococcus aureus (S. aureus). The porous (gold core)@(platinum shell) nanozymes (Au@PtNEs) as the signal labels show highly efficient peroxidase mimetic activity and arerobust. For the sake of simplicity the detection involved the use of a vancomycin-immobilized magnetic bead (MB) and aptamer-functionalized Au@PtNEs for dual-recognition detection in the presence of S. aureus.In addition, we designed a magnetic plate to fit the 96-well microplate to ensure consistent magnetic properties of each well, which can quickly remove unreacted Au@PtNEs and sample matrix while avoiding tedious washing steps. Subsequently, Au@PtNEs catalyze hydrogen peroxide (H2O2) to oxidize 3,3',5,5'-tetramethylbenzidine (TMB) generating a color signal. Finally, the developed Au@PtNEs-based dual-recognition washing-free colorimetric assay displayed a response in the range of S. aureus of 5 × 101-5 × 105 CFU/mL, and the detection limit was 40 CFU/mL within 1.5 h. In addition, S. aureus-fortified samples were analyzed to further evaluate the performance of the proposed method, which yielded average recoveries ranging from 93.66 to 112.44% and coefficients of variation (CVs) within the range 2.72-9.01%. These results furnish a novel horizon for the exploitation of a different mode of recognition and inexpensive enzyme-free assay platforms as an alternative to traditional enzyme-based immunoassays for the detection of other Gram-positive pathogenic bacteria.

MXene/Carbon Dots Nanozyme Composites for Glutathione Detection and Tumor Therapy.

Co-N-CDs-based MXene nanocomposites (MXene@PDA/Co-N-CDs) were constructed by decorating Co-N-CDs on polydopamine-functionalized MXene nanosheets. Both Co-N-CDs and MXene nanosheets have peroxidase-like activity; when the two materials are combined to form MXene@PDA/Co-N-CDs nanocomposites, the peroxide-like activity can be further enhanced. MXene@PDA/Co-N-CDs could oxidize the substrate 3,3'5,5'-tetramethylbenziline (TMB) to form ox-TMB, as confirmed by detecting the absorption of the blue products. A highly selective colorimetric biosensor was developed for the determination of glutathione (GSH) in the concentration range of 0.3 to 20 µM with a lower detection limit (LOD) of 0.12 µM, which realized the accurate detection of GSH in human serum and urine samples. Moreover, in the tumor microenvironment, MXene@PDA/Co-N-CDs could catalyze hydrogen peroxide to produce hydroxyl free radicals and produce a photothermal effect under the exposure of NIR-I irradiation. The catalytic activity of MXene@PDA/Co-N-CD nanocomposites was fully achieved for the death of cancer cells through photothermal/photodynamic synergistic therapy. The MXene@PDA/Co-N-CDs nanozyme offers multiple applications in GSH detection and tumor therapy.

Enzyme-Like Photocatalytic Octahedral Rh/Ag2MoO4 Accelerates Diabetic Wound Healing by Photo-Eradication of Pathogen and Relieving Wound Hypoxia.

The harsh environment of diabetic wounds, including bacterial infection and wound hypoxia, is not conducive to wound healing. Herein, an enzyme-like photocatalytic octahedral Rh/Ag2MoO4 is developed to manage diabetic-infected wounds. The introduction of Rh nanoparticles with catalase-like catalytic activity can enhance the photothermal conversion and photocatalytic performance of Rh/Ag2MoO4 by improving near-infrared absorbance and promoting the separation of electron-hole pairs, respectively. Rh/Ag2MoO4 can effectively eliminate pathogens through a combination of photothermal and photocatalytic antibacterial therapy. After bacteria inactivation, Rh/Ag2MoO4 can catalyze hydrogen peroxide to produce oxygen to alleviate the hypoxic environment of diabetic wounds. The in vivo treatment effect demonstrated the excellent therapeutic performance of Rh/Ag2MoO4 on diabetic infected wounds by removing infectious pathogens and relieving oxygen deficiency, confirming the potential application of Rh/Ag2MoO4 in the treatment of diabetic infected wounds.

Role of alumina particles in chemical-mechanical synergies in ruthenium polishing

Abrasive particles are usually considered to only play a "mechanical wear" role in the metal chemical mechanical polishing (CMP) process, neglecting their influence on chemical reactions. This study reveals the chemical role of Al2O3 particles in ruthenium (Ru) CMP by comparing the properties and polishing performance of Al2O3-SiO2 mixed slurry and pure SiO2 slurry. Several testing methods are used to investigate the mechanical and chemical actions of Al2O3 particles, including particle size distribution, Zeta potential, electrochemical reaction kinetics, oxide layer property and hydroxyl radical detection test. The results indicate that Al2O3 particles enhance the mechanical action by reducing the Zeta potential, and promote the chemical action by catalyzing hydrogen peroxide to produce hydroxyl radical (Fenton-like reaction) on Ru surface. These increase the material removal rate of Ru CMP with mixed slurry by nearly 5 times, while the surface roughness decreases by 60 %. The mechanism of chemical reaction promoted by increasing the hydroxyl radical concentration on Ru surface is confirmed from the aspects of increased corrosion current, oxide layer thickness and proportion of higher-valence Ru oxide (RuO2) in the oxide layer. Among them, the thickened oxide layer is a significant factor contributing to the substantial improvement in the material removal rate of Ru and the reduction in surface roughness. This study enhances the understanding of the chemical-mechanical synergistic mechanism of abrasive particles in metal polishing and elucidates the principle of this mechanism on promoting material removal and surface quality. It also provides new research ideas and theoretical guidance for efficient and high-quality metal polishing.

Iron ion catalyzed hydrogen peroxide pretreatment for bio‐jet fuel production from straw biomass

AbstractBACKGROUNDThe development of efficient and green pretreatment pathway is of great significance for promoting biofuel production from lignocellulosic waste. The purpose of this work was to evaluate that iron ion‐catalyzed hydrogen peroxide pretreatment can be used as an environmentally friendly pretreatment way for bio‐jet fuel production using straw.RESULTSThe effects of iron ion‐catalyzed hydrogen peroxide pretreatment (Fe‐HP) on the enzymatic hydrolysis, fermentation and bio‐jet fuel production using straw were investigated. It was found that the iron ion‐catalyzed hydrogen peroxide pretreatment significantly improved the enzymatic hydrolysis and fermentation efficiency of straw biomass. Subsequently, the directional catalytic transformation of straw‐derived fermentation broth to bio‐jet fuels was achieved using a dual functional catalyst (HSAPO34/NiHBET). High conversion (94.9%) and good jet‐fuel selectivity (77.3%) were obtained in the conversion process of straw. On account of the biomass characterization and the analysis of reactive oxygen species during the Fe‐HP pretreatment, the role and mechanism of the Fe‐HP pretreatment was addressed.CONCLUSIONThe Fe‐HP pretreatment can be used as an environmentally friendly pretreatment way for jet fuel production from straw biomass. Fe‐HP pretreatment increased sugar yield and sugar concentration during enzymatic hydrolysis, which was beneficial for subsequent fermentation and bio‐jet fuel production. The reactive oxygen species take a prominent role in the Fe‐HP pretreatment of lignocellulose. © 2024 Society of Chemical Industry (SCI).

A Novel Nanozyme to Enhance Radiotherapy Effects by Lactic Acid Scavenging, ROS Generation, and Hypoxia Mitigation.

Uveal melanoma (UM) is a leading intraocular malignancy with a high 5-year mortality rate, and radiotherapy is the primary approach for UM treatment. However, the elevated lactic acid, deficiency in ROS, and hypoxic tumor microenvironment have severely reduced the radiotherapy outcomes. Hence, this study devised a novel CoMnFe-layered double oxides (LDO) nanosheet with multienzyme activities for UM radiotherapy enhancement. On one hand, LDO nanozyme can catalyze hydrogen peroxide (H2O2) in the tumor microenvironment into oxygen and reactive oxygen species (ROS), significantly boosting ROS production during radiotherapy. Simultaneously, LDO efficiently scavenged lactic acid, thereby impeding the DNA and protein repair in tumor cells to synergistically enhance the effect of radiotherapy. Moreover, density functional theory (DFT) calculations decoded the transformation pathway from lactic to pyruvic acid, elucidating a previously unexplored facet of nanozyme activity. The introduction of this innovative nanomaterial paves the way for a novel, targeted, and highly effective therapeutic approach, offering new avenues for the management of UM and other cancer types.

Sprayable Diacetylene-Containing Amphiphile Coatings for Visual Detection of Gas-Phase Hydrogen Peroxide

Colorimetric chemical sensing of target gases, such as hydrogen peroxide vapors, is an evolving area of research that implements responsive materials that undergo molecule-specific interaction, resulting in a visible color change. Due to the intuitive nature of an observable color change, such sensing systems are particularly desirable as they can be widely deployed at low cost and without the need for complex analytical instrumentation. In this work, we describe our development of a new spray-on sensing material that can provide a colorimetric response to the presence of a gas-phase target, specifically hydrogen peroxide vapor. By providing a cumulative response over time, we identified that part per million concentrations of hydrogen peroxide vapor can be detected. Specifically, we make use of iron chloride-containing formulations to enable the catalysis of hydrogen peroxide to hydroxyl radicals that serve to initiate polymerization of the diacetylene-containing amphiphile, resulting in a white to blue color transition. Due to the irreversible nature of the color change mechanism, the cumulative exposure to hydrogen peroxide over time is demonstrated, enabling longitudinal assessment of target exposure with the same coatings. The versatility of this approach in generating a colorimetric response to hydrogen peroxide vapor may find practical applications for environmental monitoring, diagnostics, or even industrial safety.

Ultrasmall copper-based nanoplatforms for NIR-II light-triggered photothermal/ photodynamic and amplified nanozyme catalytic therapy of hypoxic tumor

The clinical applications of the photothermal therapy (PTT) and photodynamic therapy (PDT) are restricted by the limited tissue penetration depth of excitation light, while the enzyme catalysis therapy is hindered on account of the low treatment efficiency. Herein, we modify artificial nanozyme Pt nanoparticles on the surface of CuCo2S4 nanoparticles to prepare ultrasmall copper-based ternary bimetallic chalcogenides CuCo2S4-Pt-PEG nanocomposites for PTT/PDT/enzyme catalysis synergistic therapy. The as-fabricated CuCo2S4-Pt-PEG nanocomposites display peroxidase (POD)-like and catalase (CAT)-like activities, which can catalyze hydrogen peroxide to emerge highly toxic hydroxyl radicals and oxygen, respectively. The integration of Pt nanozyme significantly improves the POD-like and CAT-like activity of CuCo2S4 −PEG that can produce more hydroxyl radicals and oxygen to improve the effects of PDT. Furthermore, the nanocomposites exhibit outstanding photothermal properties derived from the enhanced photothermal conversion efficiency (η = 78.46 %) exposed to 1064 nm NIR-II light irradiation with a low power density (0.8 W cm−2). In particular, the photothermal performance of CuCo2S4-Pt-PEG significantly enhances the enzyme-like activity. Additionally, the T1-weighted magnetic resonance and photoacoustic imaging endow CuCo2S4-Pt-PEG with the advantages of guiding the treatment process. The synergistic treatment demonstrates significant anticancer treatment efficiency while also elicits immune response that suppressed metastasis. This study could further promote the application of ternary bimetallic chalcogenides in cancer diagnosis and treatment.

Interplay between Catalyst Corrosion and Homogeneous Reactive Oxygen Species in Electrochemical Ozone Production.

Electrochemical ozone production (EOP), a six-electron water oxidation reaction, offers promising avenues for creating value-added oxidants and disinfectants. However, progress in this field is slowed by a dearth of understanding of fundamental reaction mechanisms. In this work, we combine experimental electrochemistry, spectroscopic detection of reactive oxygen species (ROS), oxygen-anion chemical ionization mass spectrometry, and computational quantum chemistry calculations to determine a plausible reaction mechanism on nickel- and antimony-doped tin oxide (Ni/Sb-SnO2, NATO), one of the most selective EOP catalysts. Antimony doping is shown to increase the conductivity of the catalyst, leading to improved electrochemical performance. Spectroscopic analysis and electrochemical experiments combined with quantum chemistry predictions reveal that hydrogen peroxide (H2O2) is a critical reaction intermediate. We propose that leached Ni4+ cations catalyze hydrogen peroxide into solution phase hydroperoxyl radicals (•OOH); these radicals are subsequently oxidized to ozone. Isotopic product analysis shows that ozone is generated catalytically from water and corrosively from the catalyst oxide lattice without regeneration of lattice oxygens. Further quantum chemistry calculations and thermodynamic analysis suggest that the electrochemical corrosion of tin oxide itself might generate hydrogen peroxide, which is then catalyzed to ozone. The proposed pathways explain both the roles of dopants in NATO and its lack of stability. Our study interrogates the possibility that instability and electrochemical activity are intrinsically linked through the formation of ROS. In doing so, we provide the first mechanism for EOP that is consistent with computational and experimental results and highlight the central challenge of instability as a target for future research efforts.

Se site targeted-two circles antioxidant in GPx4–like catalytic peroxide degradation by polyphenols (−)-epigallocatechin gallate and genistein using SERS

A Se site targeted-two circles antioxidant of polyphenols EGCG and genistein in glutathione peroxidase 4 (GPx4)–like catalytic peroxide H2O2 and cumene hydroperoxide degradation was demonstrated by surface-enhanced Raman scattering (SERS). Se atom's active center is presenting a ‘low-oxidation’ and a ‘high-oxidation’ catalytic cycle. The former is oxidized to selenenic acid (SeO−) with a Raman bond at 619/ 610 cm−1 assigned to the νO − Se by the hydroperoxide substrate at 544/ 551 cm−1 assigned to ωHSeC decreased. Under oxidative stress, the enzyme shifted to ‘high-oxidation’ catalytic cycle, in which GPx4 shuttles between R-SeO− and R-SeOO− with a Raman intensity of bond at 840/ 860 cm−1 assigned to νOSe. EGCG could act as a reducing agent both in H2O2 and Cu-OOH degradation, while, genistein can only reduce Cu-OOH, because it binds more readily to the selenium site in GPx4 than EGCG with a closer proximity, therefore may affect its simultaneous binding to coenzymes.