Determination of persulfate based on the principle of the oxidation of chloride ion.

Persulfate (PS) is a widely used oxidant for the chemical oxidation of organic pollutants. The accurate measurement of PS concentration is crucial for the practical application process. The iodometry is the most recommended method for PS determination, and its principle is based on the redox reaction between S2O82- and iodide ions. However, hydrogen peroxide (H2O2), an important intermediate product in the process of PS use, often leads to abnormally high determination concentrations of PS. Given this, a novel method was developed for the determination of PS based on the principle of the oxidation of chloride ion (Cl-). The concentration of PS is calculated according to the consumption of Cl- concentration, which is not disturbed by H2O2. The optimized test conditions were explored as: C(H+) = 2 mol/L, T = 80℃, C(Cl-):C(PS) = 4:1 and t = 30 min. Under the optimized conditions, the limit of detection and the limit of quantification of PS concentration determined by this method were 0.26 and 0.85 g/L, respectively. And the linear range of the PS determination was 1-100 g/L with an error of 0.53%-12.06%. The spike recovery rate for determining PS concentration in the actual wastewater ranged from 94.07%-109.52%. Interfering factors such as H2O2, Fe3+, MnO2 and natural organic matter had almost no effect on the results. This method could not only accurately determine the concentration of PS in industrial wastewater, but also determine the purity of PS industrial products.

Construction of a novel Au@Os mediated TMB-H2O2 platform with dual-signal output for rapid and accurate detection of ziram in food.

The 3,3',5,5'-tetramethylbenzidine-H2O2 (TMB-H2O2) platform has gained widespread use for rapid detection of various analytes in foods. However, the existing TMB-H2O2 platforms suffer from limited accuracy, as their signal output is confined to the visible region, which is prone to interference from various food colorants in real samples. To address this challenge, a novel Au@Os-mediated TMB-H2O2 platform is developed for both rapid and accurate detection of analytes in foods. The prepared Au@Os NPs exhibit remarkable peroxidase-like activity, making the platform display dual absorption peaks in visible and near-infrared (NIR) regions, respectively. This Au@Os-mediated TMB-H2O2 platform exhibited three linear ranges across different concentrations of ziram from 1-100, 150-600, and 800-2000 nM with limit of detection (LOD) 7.9 nM and limit of quantification (LOQ) 24.15 nM respectively. Further, the Au@Os-mediated TMB-H2O2 platform was also used for rapid and accurate detection of ziram in real food samples like apple, tomato, and black tea.

Synthesis of histidine, serine and folic acid-functionalized and boron and iron-doped graphene quantum dot with excellent optical behavior and peroxidase-like activity for colorimetric and fluorescence detection of H2O2 in food.

Low fluorescence under visible light excitation and catalytic activity limit many applications of graphene quantum dots in optical detection, biosensing, catalysis and biomedical. The paper reports design and synthesis of histidine, serine and folic acid-functionalized and boron and iron-doped graphene quantum dot (Fe/B-GQD-HSF). The Fe/B-GQD-HSF shows excellent fluorescence behavior and peroxidase-like activity. Excitation of 330 nm ultraviolet light produces the strongest blue fluorescence and excitation of 480 nm visible light produces the strongest yellow fluorescence. The specific activity reaches 92.67 U g-1, which is higher than that of other graphene quantum dots. The Fe/B-GQD-HSF can catalyze oxidation of 3,3',5,5'-tetramethylbenzidine with H2O2 to form blue compound. Based on this, it was used for colorimetric and fluorescence detection of H2O2. The absorbance at 652 nm linearly increases with the increase of H2O2 concentration between 0.5 and 100 µM with detection limit of 0.43 µM. The fluorescence signal linearly decreases with the increase of H2O2 concentration between 0.05 and 100 µM with detection limit of 0.035 µM. The analytical method has been satisfactorily applied in detection of H2O2 in food. The study also paves one way for design and synthesis of functional graphene quantum dots with ideal fluorescence behavior and catalytic activity.

Ultrasmall iridium-encapsulated porphyrin metal-organic frameworks for enhanced photodynamic/catalytic therapy by producing reactive oxygen species storm.

Transition metal-coordinated porphyrin metal-organic frameworks (MOFs) were perspective in photodynamic therapy (PDT) and catalytic therapy. However, the tumor hypoxia and the insufficient endogenous hydrogen peroxide (H2O2) seriously limited their efficacies. Herein, by encapsulating ultrasmall iridium (Ir) and modifying glucose oxidase (GOx), an iron-coordinated porphyrin MOF (Fe-MOF) nanoplatform (Fe-MOF@Ir/GOx) was designed to strengthen PDT/catalytic therapy by producing reactive oxygen species (ROS) storm. In this nanoplatform, Fe-MOF showed glutathione (GSH)-responsive degradation, by which porphyrin, GOx and ultrasmall Ir were released. Moreover, ultrasmall Ir possessed dual-activities of catalase (CAT)-like and peroxidase (POD)-like, which provided sufficient oxygen (O2) to enhance PDT efficacy, and hydroxyl radical (·OH) production was also improved by combining Fenton reaction of Fe2+. Further, GOx catalyzed endogenous glucose produced H2O2, also reduced pH value, which accelerated Fenton reaction and resulted in generation of ROS storm. Therefore, the developed Fe-MOF@Ir/GOx nanoplatform demonstrated enhanced PDT/catalytic therapy by producing ROS storm, and also provided a promising strategy to promote degradation/metabolism of inorganic nanoplatforms.

Cyclic catalysis of intratumor Fe3+/2+ initiated by a hollow mesoporous iron sesquioxide nanoparticle for ferroptosis therapy of large tumors.

Numerous nanoparticles have been utilized to deliver Fe2+ for tumor ferroptosis therapy, which can be readily converted to Fe3+via Fenton reactions to generate hydroxyl radical (•OH). However, the ferroptosis therapeutic efficacy of large tumors is limited due to the slow conversion of Fe3+ to Fe2+via Fenton reactions. Herein, a strategy of intratumor Fe3+/2+ cyclic catalysis is proposed for ferroptosis therapy of large tumors, which was realized based on our newly developed hollow mesoporous iron sesquioxide nanoparticle (HMISN). Cisplatin (CDDP) and Gd-poly(acrylic acid) macrochelates (GP) were loaded into the hollow core of HMISN, whose surface was modified by laccase (LAC). Fe3+, CDDP, GP, and LAC can be gradually released from CDDP@GP@HMISN@LAC in the acidic tumor microenvironment. The intratumor O2 can be catalyzed into superoxide anion (O2•-) by LAC, and the intratumor NADPH oxidases can be activated by CDDP to generate O2•-. The O2•- can react with Fe3+ to generate Fe2+, and raise H2O2 level via the superoxide dismutase. The generated Fe2+ and H2O2 can be fast converted into Fe3+ and •OH via Fenton reactions. The cyclic catalysis of intratumor Fe3+/2+ initiated by CDDP@GP@HMISN@LAC can be used for ferroptosis therapy of large tumors.

The profound review of Fenton process: What's the next step?

Fenton and Fenton-like processes, which could produce highly reactive species to degrade organic contaminants, have been widely used in the field of wastewater treatment. Therein, the chemistry of Fenton process including the nature of active oxidants, the complicated reactions involved, and the behind reason for its strongly pH-dependent performance, is the basis for the application of Fenton and Fenton-like processes in wastewater treatment. Nevertheless, the conflicting views still exist about the mechanism of the Fenton process. For instance, reaching a unanimous consensus on the nature of active oxidants (hydroxyl radical or tetravalent iron) in this process remains challenging. This review comprehensively examined the mechanism of the Fenton process including the debate on the nature of active oxidants, reactions involved in the Fenton process, and the behind reason for the pH-dependent degradation of contaminants in the Fenton process. Then, we summarized several strategies that promote the Fe(II)/Fe(III) cycle, reduce the competitive consumption of active oxidants by side reactions, and replace the Fenton reagent, thus improving the performance of the Fenton process. Furthermore, advances for the future were proposed including the demand for the high-accuracy identification of active oxidants and taking advantages of the characteristic of target contaminants during the degradation of contaminants by the Fenton process.

Valence-engineered catalysis-selectivity regulation of molybdenum oxide nanozyme for acute kidney injury therapy and post-cure assessment.

The optimization of the enzyme-like catalytic selectivity of nanozymes for specific reactive oxygen species (ROS)-related applications is significant, and meanwhile the real-time monitoring of ROS is really crucial for tracking the therapeutic process. Herein, we present a mild oxidation valence-engineering strategy to modulate the valence states of Mo in Pluronic F127-coated MoO3-x nanozymes (denoted as MF-x, x: oxidation time) in a controlled manner aiming to improve their specificity of H2O2-associated catalytic reactions for specific therapy and monitoring of ROS-related diseases. Experimentally, MF-0 (Mo average valence 4.64) and MF-10 (Mo average valence 5.68) exhibit exclusively optimal catalase (CAT)- or peroxidase (POD)-like activity, respectively. Density functional theory (DFT) calculations verify the most favorable reaction path for both MF-0- and MF-10-catalyzed reaction processes based on free energy diagram and electronic structure analysis, disclosing the mechanism of the H2O2 activation pathway on the Mo-based nanozymes. Furthermore, MF-0 poses a strong potential in acute kidney injury (AKI) treatment, achieving excellent therapeutic outcomes in vitro and in vivo. Notably, the ROS-responsive photoacoustic imaging (PAI) signal of MF-0 during treatment guarantees real-time monitoring of the therapeutic effect and post-cure assessment in vivo, providing a highly desirable non-invasive diagnostic approach for ROS-related diseases.

Au@Pt nanoparticles-based signal-enhanced lateral flow immunoassay for ultrasensitive naked-eye detection of SARS-CoV-2.

With SARS-CoV-2 N protein as a model target, a signal-enhanced LFIA based on Au@Pt nanoparticles (NPs) as labels is proposed. This Au@Pt NPs combined the distinguished localized surface plasma resonance (LSPR) effect of Au NPs and the ultrahigh peroxidase-like catalytic activity of Pt NPs. Au@Pt NPs could trigger substrate chromogenic reaction, generating a color signal orders of magnitude darker than their intrinsic color. In the detection, after the coloration of the strips, 3,3',5,5'-tetramethylbenzidine (TMB) and H2O2 were added, and a dark blue chelate (OxTMB) was produced soon, enhancing the band color significantly. After the signal amplification, the naked-eye detection limit for N protein reached 40 pg/mL. The detection sensitivity enhanced more than 1000 times than that without signal amplification. Compared with mainstream LFIA requiring complex readout instruments, the Au@Pt-based LFIA achieved a comparable sensitivity using naked eyes detection. This point is crucial, especially for unprofessional users or low-resource areas. Hence, this signal-enhanced LFIA may serve as a sensitive, cost-effective, and user-friendly detection method. It can shorten the testing window period and help identify early infections.

Two-dimensional black phosphorus/platinum catalase-like nanozyme-based Fenton reaction-mediated dual-mode immunoassays for the detection of enrofloxacin.

Hydrogen peroxide-based Fenton reaction can effectively degrade many small-molecule fluorescent dyes, leading to notable alterations in fluorescence signals. Additionally, the two-dimensional black phosphorus/platinum nanocomposite (BP/Pt) demonstrates exceptional catalase (CAT) characteristics. Based on these, a colorimetric-fluorescence dual-mode signal output pattern based on BP/Pt-Fenton reaction-rhodamine B tandem reaction system is reported. The physical adsorption property of the BP/Pt nanozymes was utilized to couple with antibodies, thus constructing a novel dual-mode nanozyme-based immuno-sensing assay (NISA). By using the migratory antibiotic enrofloxacin (ENR) as the target, the NISA provided highly sensitive detection with the detection limits of 0.058 ng/mL for colorimetric-mode and 0.025 ng/mL for fluorescence-mode and achieved accurate quantitative detection in environmental water and crucian carp samples. This work provides an innovative design for monitoring antibiotics in the environment and broadens the idea for the application of nanozymes and Fenton systems in immunosensing assays.

An enzymatic reaction-based SERS saliva analysis microporous array chip for chiral differentiation and high-throughput detection of D-amino acids.

A Raman-active boronate modified surface-enhanced Raman scattering (SERS) microporous array chip based on the enzymatic reaction was constructed for reliable, sensitive, and quantitative monitoring of D-Proline (D-Pro) and D-Alanine (D-Ala) in saliva. Initially, 3-mercaptophenylboronic acid (3-MPBA) was bonded to Au-coated Si nanocrown arrays (Au/SiNCA) via Au-S bonding. Following this, H2O2 obtained from D-amino acid oxidase (DAAO)-specific catalyzed D-amino acids (D-AAs) further reduced 3-MPBA to 3-hydroxythiophenol (3-HTP) with a new Raman peak at 882 cm-1. Meanwhile, the original characteristic peak at 998 cm-1 remained unchanged. Therefore, the I882/I998 ratio increased with increasing content of D-AAs in the sample to be tested, allowing D-AAs to be quantitatively detected. The Au/SiNCA with large-area periodic crown structure prepared provided numerous, uniform "hot spots," and the microporous array chip with 16 detection units was employed as the platform for SERS analysis, realizing high-throughput, high sensitivity, high specificity and high-reliability quantitative detection of D-AAs (D-Pro and D-Ala). The limits of detection (LOD) were down to 10.1 µM and 13.7 µM throughout the linear range of 20-500 µM. The good results of the saliva detection suggested that this SERS sensor could rapidly differentiate between early-stage gastric cancer patients and healthy individuals.

Hyaluronic acid modified Cu/Mn-doped metal-organic framework nanocatalyst for chemodynamic therapy.

Chemodynamic therapy (CDT) is a new method for cancer treatment that produces highly toxic reactive oxygen species (ROS) in the tumor microenvironment to induce cancer cell apoptosis or necrosis. However, the therapeutic effect of CDT is often hindered by intracellular H2O2deficiency and the activity of antioxidants such as glutathione (GSH). In this study, a nano-catalyst HCM was developed using a self-assembled Cu/Mn-doped metal-organic framework, and its surface was modified with hyaluronic acid to construct a tumor-targeting CDT therapeutic agent with improved the efficiency and specificity. Three substances HHTP (2, 3, 6, 7, 10, 11-hexahydroxybenzophenanthrene), Cu2+, and Mn2+were shown to be decomposed and released under weakly acidic conditions in tumor cells. HHTP produces exogenous H2O2in the presence of oxygen to increase the H2O2content in tumors, Cu2+reduces GSH content and generates Cu+in the tumor, and Cu+and Mn2+catalyze H2O2to produce ∙OH in a Fenton-like reaction. Together, these three factors change the tumor microenvironment and improve the efficiency of ROS production. HCM showed selective and efficient cytotoxicity to cancer cells, and could effectively inhibit tumor growthin vivo, indicating a good CDT effect.

Highly sensitive ECL detection of miRNA based on self-generated coreactant and target-induced catalyzed hairpin assembly.

BACKGROUND: Recently, various techniques have been developed to accurately and sensitively detect tumor biomarkers for the early diagnosis and effective therapy of cancer. The electrochemiluminescence (ECL) method holding outstanding features including high sensitivity, ease of operation, and spatiotemporal controllability exhibited great potential for DNA/RNA detection, immunoassay, cancer cell detection, and environmental analysis. However, a glaring problem of ECL approaches is that the layer-by-layer modification on the electrode leads to poor stability and sensitivity of the sensors. Therefore, new simple and efficient methods for electrode modification which can effectively improve the ECL signal have attracted more and more research interests. RESULTS: Based on the dual amplification strategy of target-induced CHA and nanocomposite probes leading to self-generated co-reactant (H2O2), we proposed a highly sensitive miRNA-ECL detection system. The introduction of the target miRNA-21 triggers the CHA cycle amplification of DNA1 and biotin-modified DNA2, releasing the target miRNA-21 sequence for the target cycle reaction. After the reaction, the newly introduced DNA2 was combined with Au NPs modified with SA and Glucose oxidase (GOD). In the presence of oxygen, glucose was decomposed by GOD to produce H2O2, and then H2O2 was immediately catalyzed by the Hemin/G-quadruplex at the double-stranded end of the CHA product to produce a large amount of O2-•. As a co-reactant of luminol, the ECL signal was significantly enhanced, thereby achieving highly sensitive detection of miRNA-21 content and obtaining a low detection limit of 0.65 fM. The high specificity of the ECL biosensor was also proved by base mismatch. SIGNIFICANCE: Compared with other current detection methods, this sensor can achieve quantitative analysis of other target analytes by flexibly changing the probe DNA sequence, and provide a new feasible solution for the detection of tumor-associated markers. Benefiting from the improved sensitivity and selectivity, the proposed biosensing platform is expected to provide a new strategy for biomarkers analysis and outstanding prospect for further clinical application.

Probing trace of intracellularly-originated hydrogen peroxide based Pt-Cd bimetallic nanozyme on an enzyme-free electrochemical sensor.

BACKGROUND: Measurement of endogenous cellular hydrogen peroxide (H2O2) can provide information on cellular status, and help to understand cellular metabolism and signaling processes, thus contributing to elucidation of disease mechanisms and new diagnostics/therapeutic approaches. RESULTS: In this work, Pt-Cd bimetallic nanozyme was successfully prepared via the solvothermal synthetic method for sensitive detection of H2O2. The synthesized Pt-Cd bimetallic nanozyme could exhibited good electrochemical activity. Then, the materials were analyzed for the electrochemical properties and catalytic properties of H2O2 by cyclic voltammetry and chronoamperometry, respectively. Results indicated that the synthesized nanozyme had superior sensitivity (295 µA⸳mM-1⸳cm-2) and selectivity toward H2O2 with a detection limit of 0.21 µM. Further, the Pt-Cd bimetallic nanozyme displayed good electrochemical properties compared to platinum catalysts alone. The application was extended to determine the produced H2O2 from human hepatocellular carcinoma cells (HepG2) and normal hepatocyte (LO2) samples after ascorbic acid stimulation, thus enabling the early warning of cellular carcinogenesis. SIGNIFICANCE: This strategy promises simple, rapid, inexpensive and effective electrochemical sensing and provides a new pathway for the synthesis of bimetallic nanozymes to construct an electrochemical sensor for the sensitive detection of H2O2.

Effect of immune-boosting beverage, energy beverage, hydrogen peroxide superior, polishing methods and fine-grained dental prophylaxis paste on color of CAD-CAM restorative materials.

BACKGROUND: The effect of an immune-boosting beverage (SAM) containing Sambucus Nigra, an energy beverage (ENE), an in-office bleaching (BLE) agent with 25% hydrogen peroxide superior, glazing (GLA) or polishing (POL) methods, and professional dental prophylaxis (PDP) on the color of CAD-CAM restorative materials is unknown. METHODS: In total 210 specimens were prepared, consisting of CAD-CAM feldspathic (FC), zirconia-reinforced lithium disilicate ceramic (ZLS) and hybrid ceramic (HC). The ceramic specimens were divided according to the polishing methods of glazing (GLA) and mechanical polishing (POL). All materials were divided into two groups: with and without BLE. A 25% hydrogen peroxide superior (HPS) gel was used for BLE. After the baseline (BAS) measurement, the specimens were immersed in 3 different beverages (distilled water (DIS), SAM, ENE). After 28 days, a fine-grained (RDA 7) prophylaxis paste was applied. Statistical analysis of ∆E00 color difference values was performed by 3-way ANOVA and Bonferroni test (α = 0.05). RESULTS: The effect of all other actions except material-BLE-beverage on color for BAS-Day 28 was statistically different (p < 0.05). The effect of material, material-BLE, beverage on color for Day 28-PDP was statistically different (p < 0.05). After 28 days, the lowest color change was found in FC-GLA and HC immersed in DIS (p = 0.0001) and the highest in FC-POL immersed in ENE (p = 0.0002). PDP was efficient in color recovery in HC immersed to DIS, ENE and SAM (p = 0.0010). For FC, HC and ZLS, BLE caused a higher color change (p < 0.0001). Regardless of the material, the highest color change for BLE-beverage was found in BLE-treated specimens immersed in ENE (p = 0.0496) and the lowest color change was found in non-BLE-treated specimens immersed in SAM (p = 0.0074). CONCLUSIONS: In materials pre-exposed to 25% HPS, the effect of PDP on color recovery was lower than in unexposed materials. After 28 days, mechanical polishing produced higher color change in FC than glazing, however, in ZLS effects of glazing and mechanical polishing on color were similar. For material/polishing method, HC was the most effective. ENE caused higher color change than DIS and SAM. PDP was more effective than ENE in restoring color to DIS- and SAM-immersed specimens.

Facile One-Pot Preparation of Polypyrrole-Incorporated Conductive Hydrogels for Human Motion Sensing.

Conductive hydrogels have been widely used in soft robotics, as well as skin-attached and implantable bioelectronic devices. Among the candidates of conductive fillers, conductive polymers have become popular due to their intrinsic conductivity, high biocompatibility, and mechanical flexibility. However, it is still a challenge to construct conductive polymer-incorporated hydrogels with a good performance using a facile method. Herein, we present a simple method for the one-pot preparation of conductive polymer-incorporated hydrogels involving rapid photocuring of the hydrogel template followed by slow in situ polymerization of pyrrole. Due to the use of a milder oxidant, hydrogen peroxide, for polypyrrole synthesis, the photocuring of the hydrogel template and the growing of polypyrrole proceeded in an orderly manner, making it possible to prepare conductive polymer-incorporated hydrogels in one pot. The preparation process is facile and extensible. Moreover, the obtained hydrogels exhibit a series of properties suitable for biomedical strain sensors, including good conductivity (2.49 mS/cm), high stretchability (>200%), and a low Young's modulus (~30 kPa) that is compatible with human skin.

Effect of protein oxidation on the structure and emulsifying properties of fish gelatin.

This study aimed to investigate the effect of oxidation on fish gelatin and its emulsifying properties. Fish gelatin was oxidized with varying concentrations of H2O2 (0-30 mM). Increased concentrations of the oxidant led to a decrease in amino acids in the gelatin, including glycine, lysine, and arginine. Additionally, the relative content of ordered secondary structure and triple helix fractions decreased. Zeta potential decreased, while particle size, surface hydrophobicity, and water contact angle increased. Regarding emulsifying behavior, oxidation promoted the adsorption of gelatin to the oil-water interface and reduced interfacial tension. With increased degrees of oxidation, the zeta potential and size of the emulsion droplets decreased. The oxidized gelatin exhibited better emulsifying activity but worse emulsifying stability. Based on these results, a mechanism for how oxidation affects the emulsifying properties of gelatin was proposed: the increase in gelatin's hydrophobicity and the decrease in triple helix structure induced by oxidation reduced the interfacial tension at the oil-water interface. This promoted protein adsorption at the oil-water interface, allowing the formation of smaller oil droplets and enhancing gelatin's emulsifying activity. However, the decrease in electrostatic repulsion between emulsion droplets and the decrease in solution viscosity increased the flocculation and aggregation of oil droplets, ultimately weakening the emulsifying stability of gelatin.

Interface coupling to improve O2 adsorption and accelerate charge separation for boosting photocatalytic performance of ZnO/ZnIn2S4 composite in H2O2 production and environmental remediation.

The key to heterogeneous photo-Fenton technology lies in the efficient generation of hydrogen peroxide (H2O2). Herein, a newly-designed ZnO/ZnIn2S4 composite with heterostructure is synthesized. Benefiting from the formation of built-in electric field, the recombination of photoinduced electrons and holes is suppressed and interfacial charge transfer resistance is reduced. Importantly, the embedding of ZnO in ZnIn2S4 can improve the hydrophobicity and create microscopic three-phase interface, thereby boosting the capture capability for O2 and providing the convenience for the occurrence of O2 reduction reaction. More interestingly, the existence of ZnIn2S4 in the ZnO/ZnIn2S4 composite can reduce the Gibbs free energy (ΔG) of key intermediate (OOH*) formation, which will accelerate the generation of H2O2. As a result, the ZnO/ZnIn2S4 composite displays excellent performance in photocatalytic H2O2 production, and the highest yield was about 897.6 µmol/g/h within 60 min under visible light irradiation. The transfer of photoinduced carriers follows the S-scheme type mechanism. The photogenerated holes can be captured by drug residues (i.e., diclofenac sodium) to accelerate H2O2 production, while generated H2O2 can combine with Fe2+ to construct photo-Fenton system for achieving the advanced degradation of diclofenac sodium, which was mainly related to the formation of OH•. Furthermore, generated H2O2 can be applied for performing the inactivation of pathogenic bacteria. In short, current work will provide a valuable reference for future research.

Revisiting the Iron(II)/Cobalt(II)-Based Homogenous Fenton-like Processes from the Standpoint of Diverse Metal-Oxygen Complexes.

The aqueous FeIV-oxo complex and FeIII-peroxy complex (e.g., ligand-assisted or interfacial FeIII-hydroperoxo intermediates) have been recognized as crucial reactive intermediates for decontamination in iron-based Fenton-like processes. Intermediates with terminal oxo ligands can undergo the oxygen atom exchange process with water molecules, whereas peroxides are unable to induce such exchanges. Therefore, these distinct metal-oxygen complexes can be distinguished based on the above feature. In this study, we identified previously unknown intermediates with a peroxy moiety and cobalt center that were generated during peroxymonosulfate (PMS) activation via aqueous CoII ions under acidic conditions. Results of theoretical calculations and tip-enhanced Raman spectroscopy revealed that the CoII ion tended to coordinate with the PMS anion to form a bidentate complex with a tetrahedral structure. These reactive cobalt intermediates were collectively named the CoII-PMS* complex. Depending on the inherent characteristics of the target contaminants, the CoII-PMS* complex can directly oxidize organic compounds or trigger PMS disproportionation to release hydroxyl radicals and sulfate radicals for collaborative decontamination. This work provides a comparative study between iron- and cobalt-based Fenton-like processes and proposes novel insights from the standpoint of diverse metal-oxygen complexes.

Sensitive colorimetric detection of glutathione in human serum based on peroxidase-like activity of chitosan-stabilized gold nanoparticles.

A colorimetric sensor for the rapid and sensitive detection of GSH was developed. The hydrothermal method was utilized to synthesize chitosan-stabilized gold nanoparticles (CS-AuNPs). The synthesized CS-AuNPs were characterized by UV-vis absorption spectroscopy, transmission electron microscopy (TEM), X-ray diffractograms (XRD), and Fourier transform infrared spectroscopy (FTIR). The CS-AuNPs are well-dispersed and possess a spherical shape with an average particle size of 10.05 ± 2.26 nm in aqueous solution. They show an intrinsic peroxidase-like activity, which could efficiently catalyze the decomposition of H2O2 to produce •OH radicals. These radicals then oxidized 3, 3´, 5, 5´-tetramethylbenzidine (TMB), resulting in the formation of the blue oxidized product oxTMB, observed a visible color change (from colorless to blue), and oxTMB had an obvious absorption peak at 652 nm. The presence of GSH could inhibit the peroxidase-like activity of CS-AuNPs, thereby reducing the formation of oxTMB. The solution's blue hue underwent a reduction in absorption intensity. Based on this fact, a novel and sensitive colorimetric sensor for detection of GSH was constructed. Under optimal conditions, the results of detection had an excellent linear relationship between the concentration of GSH and ∆A within the range 0.5 ~ 50.0 × 10-6 mol/L. The limit of detection (LOD) for GSH was 2.10 × 10-7 mol/L, which was much lower than those in most previous works. Furthermore, for detection in real human serum samples, the recoveries of GSH and the relative standard deviations (RSD) in the serum were in the range 98.40 ~ 103.32% and 1.85 ~ 3.54%, respectively. Thus, this visual colorimetric method has good precision and can be used for GSH detection in practical applications, promising in the fields of bioanalysis and illness diagnostics.

Arsenic(III) sequestration by terrestrial-derived soil protein: Roles of redox-active moieties and Fe(III).

Glomalin-related soil protein (GRSP) has demonstrated significant potential for water purification and remediation of heavy metals in soils; however, its redox reactivity for As(III) sequestration and the corresponding redox-active component are still poorly understood. This study investigated the photochemical properties of GRSP and its mechanism of oxidation/adsorption of As(III). The results showed that UV irradiation triggered electron transfer and the production of reactive oxygen species (ROS) in GRSP, thereby facilitating As(III) oxidation with promotion rates ranging from 43.34 % to 111.1 %. The oxidation of As(III) occurred both on the GRSP photoforming holes and in the ROS reaction from the oxygen reduction products of the photoforming electrons. OH• and H2O2 played an important role in the oxidation of As(III) by GRSP, especially under alkaline conditions. Moreover, the presence of Fe(III) in GRSP facilitated the formation of OH• and its the oxidation capacity towards As(III). The binding of As(III) to the -COOH, -OH, and -FeO groups on the GRSP surface occurred through surface complexation. Overall, these findings provided new insights into the roles of the redox-active moieties and Fe(III) on GRSP in the promoted oxidation of As(III), which would help to deepen our understanding of the migration and transformation of As(III) in soils.