Excellent Peroxidase-like Activity Research Articles

MoO3/MIL-125-NH2 with boosted peroxidase-like activity for electrochemical staphylococcus aureus sensing via specific recognition of bacteriophages

Herein, novel nanozyme mimics MoO3/MIL-125-NH2 were reported and conjugated with bacteriophages as a new electrochemical probe for high sensitivity and specific electrochemical detection of staphylococcus aureus. The excellent peroxidase-like activity of MoO3/MIL-125-NH2 composites was attributed to the integration of MIL-125-NH2 with MoO3, which can boost the generation of superoxide radicals (O• 2–) and thus promote the oxidation of TMB in the presence of H2O2. In this work, two bacteriophages named SapYZU04 and SapYZU10 were isolated from sewage samples by using staphylococcus aureus YZUsa12 as the host. In comparison, MoO3/MIL-125-NH2@SapYZU04 was selected as a recognition agent. The DPV current declined linearly with staphylococcus aureus YZUsa12 concentration in the range of 101−108 CFU mL−1, with a low detection limit of 16 CFU mL−1 (S/N = 3). 20 strains including 13 host strains and 7 non-host strains were used to evaluate the selectivity of the proposed sensor. Regardless of the differences in the degrees of lytic performance for phage SapYZU04, all selected host strains can be screened with merely the same DPV current. Host spectrum-oriented bacteriophage sensing is of great importance for the practical application of bacteriophage-based biosensors in the future.

A Multienzyme Reaction-Mediated Electrochemical Biosensor for Sensitive Detection of Organophosphorus Pesticides.

Ethephon (ETH), a commonly employed growth regulator, poses potential health risks due to its residue in fruits and vegetables, leading to both acute and subchronic toxicity. However, the detection accuracy of ETH is compromised by the color effects of the samples during the detection process. In this work, a multienzyme reaction-mediated electrochemical biosensor (MRMEC) was developed for the sensitive, rapid, and color-interference-resistant determination of ETH. Nanozymes Fe3O4@Au-Pt and graphene nanocomplexes (GN-Au NPs) were prepared as catalysts and signal amplifiers for MRMEC. Acetylcholinesterase (AChE), acetylcholine (ACh), and choline oxidase (CHOx) form a cascade enzyme reaction to produce H2O2 in an electrolytic cell. Fe3O4@Au-Pt has excellent peroxidase-like activity and can catalyze the oxidation of 3,3',5,5'-tetramethvlbenzidine (TMB) in the presence of H2O2, resulting in a decrease in the characteristic peak current of TMB. Based on the inhibitory effect of ETH on AChE, the differential pulse voltammetry (DPV) current signal of TMB was used to detect ETH, offering the limit of detection (LOD) of 2.01 nmol L-1. The MRMEC method effectively analyzed ETH levels in mangoes, showing satisfactory precision (coefficient of variations, 2.88-15.97%) and recovery rate (92.18-110.72%). This biosensor holds promise for detecting various organophosphorus pesticides in food samples.

A Novel Label-Free Electrochemical Immunosensor for the Detection of Thyroid Transcription Factor 1 Using Ribbon-like Tungsten Disulfide-Reduced Graphene Oxide Nanohybrids and Gold Nanoparticles.

Thyroid transcription factor 1 (TTF1) is an important cancer-related biomarker for clinical diagnosis, especially for carcinomas of lung and thyroid origin. Herein, a novel label-free electrochemical immunosensor was prepared for TTF1 detection based on nanohybrids of ribbon-like tungsten disulfide-reduced graphene oxide (WS2-rGO) and gold nanoparticles (AuNPs). The proposed immunosensor employed H2O2 as the electrochemical probe because of the excellent peroxidase-like activity of ribbon-like WS2-rGO. The introduction of AuNPs not only enhanced the electrocatalytic activity of the immunosensor, but also provided immobilization sites for binding TTF1 antibodies. The electrochemical signals can be greatly amplified due to their excellent electrochemical performance, which realized the sensitive determination of TTF1 with a wide linear range of 0.025-50 ng mL-1 and a lower detection limit of 0.016 ng mL-1 (S/N = 3). Moreover, the immunosensor exhibited high selectivity, good reproducibility, and robust stability, as well as the ability to detect TTF1 in human serum with satisfactory results. These observed properties of the immunosensor enhance its potential practicability in clinical applications. This method can also be used for the detection of other tumor biomarkers by using the corresponding antigen-antibody complex.

A novel three-stage continuous sensing platform for H2O2 and cholesterol based on CuFeS2 nanozyme: Theoretical calculation and experimental verification

It is still a challenge to establish a facile and reliable sensing platform with broad linear range. In this work, an innovative substrate concentration-regulated strategy was developed for design of three-stage continuous colorimetric sensing platform for H2O2, vastly broadening the detecting linear range of the sensor. In detail, a novel nanozymes, the hollow CuFeS2 nanospheres with excellent peroxidase-like activity was synthesized, which could catalyze the oxidation of 3,3,5,5-tetramethylbenzidine (TMB) by H2O2. Cytotoxicity test toward HUVEC and Hela cells verified the good biocompatibility of CuFeS2, guaranteeing its safety in biological applications. DFT theoretical calculation and experimental results both proved that the H2O2 adsorption capacity of CuFeS2 was higher than that of CuS and FeS. On this basis, a three-stage continuous sensing platform with broad detecting range by adjusting the concentration of TMB was developed. The proposed method was also successfully applied in detecting H2O2 in milk samples. Besides, coupled with cholesterol oxidase (ChOx), a cascade catalyzed colorimetric sensing platform for determining cholesterol had been constructed. Thus, this work not only provides the excellent performance of nanozymes, but also opens up a new avenue for designing sensing platform with extra-wide detecting range.

Critical role of zero-valent iron in the efficient activation of H2O2 for 4-CP degradation by bimetallic peroxidase-like.

Peroxidase-like based on double transition metals have higher catalytic activity and are considered to have great potential for application in the field of pollutant degradation. First, in this paper, a novel Fe0-doped three-dimensional porous Fe0@FeMn-NC-like peroxidase was synthesized by a simple one-step thermal reduction method. The doping of manganese was able to reduce part of the iron in Fe-Mn binary oxides to Fe0 at high temperatures. In addition, Fe0@FeMn-NC has excellent peroxidase-like mimetic activity, and thus, it was used for the rapid degradation of p-chlorophenol (4-CP). During the degradation process, Fe0 was able to rapidly replenish the constantly depleted Fe2+ in the reaction system and brought in a large number of additional electrons. The ineffective decomposition of H2O2 due to the use of H2O2 as an electron donor in the reduction reactions from Fe3+ to Fe2+ and from Mn3+ to Mn2+ was avoided. Finally, based on the experimental results of LC-MS and combined with theoretical calculations, the degradation process of 4-CP was rationally analyzed, in which the intermediates were mainly p-chloro-catechol, p-chloro resorcinol, and p-benzoquinone. Fe0@FeMn-NC nano-enzymes have excellent catalytic activity as well as structural stability and perform well in the treatment of simulated wastewater containing a variety of phenolic pollutants as well as real chemical wastewater. It provides some insights and methods for the application of peroxidase-like enzymes in the degradation of organic pollutants.

Generation of a specific aptamer for accurate detection of sarafloxacin based on fluorescent/colorimetric/SERS triple-readout sensor

Sarafloxacin (SAR), one of the most widely used fluoroquinolone antibiotics, is a serious threat to aquatic environments and human health due to its illegal abuse. Herein, we first screened an aptamer (SAR-1) that specifically binds to SAR using capture-SELEX technology. Based on molecular docking technology, SAR-1 was gradually truncated, and a short SAR-1a with better affinity and specificity was obtained. The optimal SAR-1a was further combined with a Pt nanoparticle (Pt NP)- decorated bimetallic Fe/Co-MOF to fabricate a multimode sensing platform for SAR determination. The Fe/Co-MOF@Pt NPs exhibited excellent peroxidase-like activity, which catalyzed the H2O2-mediated oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB), thereby enabling visual detection of SAR. Meanwhile, the generated oxTMB can also produce SERS responses and be used for the SERS detection of SAR. Moreover, the inherent fluorescence property of Fe/Co-MOF@Pt NPs enabled fluorescence detection of SAR. The designed triple-readout aptasensor showed good sensitivity for SAR detection with limits of detection of 0.125 ng/mL (fluorescent mode) and 0.05 ng/mL (colorimetric and SERS mode). The aptamer-based triple-mode sensing platform provided mutual verification of detection results in different output modes, effectively improving the assay accuracy and providing a promising tool for highly sensitive, selective, and accurate determination of SAR in daily life.

Fe3O4 nanoparticles entrapped in the inner surfaces of N-doped carbon microtubes with enhanced biomimetic activity.

Tubular structured composites have attracted great interest in catalysis research owing to their void-confinement effects. In this work, we synthesized a pair of hollow N-doped carbon microtubes (NCMTs) with Fe3O4 nanoparticles (NPs) encapsulated inside NCMTs (Fe3O4@NCMTs) and supported outside NCMTs (NCMTs@Fe3O4) while keeping other structural features the same. The impact of structural effects on the catalytic activities was investigated by comparing a pair of hollow-structured nanocomposites. It was found that the Fe3O4@NCMTs possessed a higher peroxidase-like activity when compared with NCMTs@Fe3O4, demonstrating structural superiority of Fe3O4@NCMTs. Based on the excellent peroxidase-like catalytic activity and stability of Fe3O4@NCMTs, an ultra-sensitive colorimetric method was developed for the detection of H2O2 and GSH with detection limits of 0.15 μM and 0.49 μM, respectively, which has potential application value in biological sciences and biotechnology.

PdMo bimetallene nanozymes for photothermally enhanced antibacterial therapy and accelerated wound healing.

Although antibacterial platforms involving nanozymes have been extensively investigated, there are still problems of poor reactive oxygen species generation efficiency and obstinate bacterial biofilms. Developing a nanozyme-photothermal therapy nanoplatform with superior sterilization effects and minimal side effects would be a good alternative for completely eliminating bacteria and biofilms. Herein, an ultrathin PdMo bimetallene nanozyme with a planar topology and boosted metal utilization, exhibiting excellent photothermal and peroxidase-like activity, is designed for synergistic nanozyme-photothermal sterilization applications and accelerated wound healing. The superior catalytic activity of PdMo bimetallene nanozymes could convert a biosafe concentration of hydrogen peroxide (H2O2) into large quantities of toxic hydroxyl radicals (•OH) under laser irradiation, enhancing bacterial membrane permeability and thermal sensitivity for efficient removal of bacteria and biofilms. In addition, PdMo bimetallene presents a good wound-healing ability according to the results of fibroblast proliferation and collagen deposition with minor side effects. This work would provide an innovative avenue for developing metallene-based nanozymes for biomedical applications.

Peroxidase activity of a Cu-Fe bimetallic hydrogel and applications for colorimetric detection of ascorbic acid.

A Cu-Fe bimetallic hydrogel (2-QF-CuFe-G) was constructed through a simple method. The 2-QF-CuFe-G metallohydrogel possesses excellent peroxidase-like activity to catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H2O2. The catalytic mechanism was confirmed by the addition of •OH radical scavenger isopropyl alcohol (IPA), tert-butyl alcohol (TBA) and ˙OH trapping agent terephthalic acid (TA). Remarkably, the resultant blue ox-TMB system can be used to selectively and sensitively detect ascorbic acid (AA) with an LOD of 0.93 μM in the range of 4-36 μM through the colorimetric method. Moreover, the assay based on the 2-QF-CuFe-G metallohydrogel can be successfully applied to detect AA in fresh fruits.

In situ Hg2+ improved the peroxidase-like activity and triggered "ON" the oxidase-like activity of yolk-shell Co3S4 microspheres for the detection of Hg2.

Exploring highly active nanozymes is an important task to realize the real-time detection of some heavy metal ions in water. In this work, yolk-shell Co3S4 microspheres have been verified to possess excellent peroxidase-like activity, which can be further improved by adding Hg2+. Very interestingly, Hg2+ can trigger "ON" the oxidase-like activity of Co3S4 microspheres. The dual peroxidase-/oxidase-like activity of the yolk-shell Co3S4 microspheres is evaluated by using the chromogenic substrate 3,3',5,5'-tetramethylbenzidine (TMB). Furthermore, comprehensive studies verify that the enhanced peroxidase-like activity, together with the "ON" oxidase-like activity of the yolk-shell Co3S4 microspheres, is attributed to the in situ generation of HgS on the surface of Co3S4 microspheres and then the release of more active sites. Importantly, the in situ generated HgS on the surface of Co3S4 microspheres can form a heterojunction, which also accelerates the catalytic process. During the catalytic reaction, some active species (O2- and h+) can be detected by ESR. Thus, a colorimetric sensing platform based on Hg2+-triggered signal amplification has been successfully constructed, which can be validated by the detection of Hg2+ residue in environmental water.

Chitosan-chelated carbon dots-based nanozyme of extreme stability with super peroxidase activity and antibacterial ability for wound healing

Bacterial infection often leads to failed wound healing, causing one-third of death cases globally. However, antibacterial nanomaterials and natural enzymes face limitations including low antibacterial efficiency, lack of catalytic performance, low safety, and instability. Therefore, a new Fe/N-doped chitosan-chelated carbon dot-based nanozyme CS@Fe-N CDs was developed, which showed multiple advantages such as highly efficient antibacterial activity, excellent peroxidase-like activity, high stability, and high biocompatibility, shortening the wound healing time. The ultra-small (6.14 ± 3.38 nm) CS@Fe-N CDs nanozyme accelerated the H2O2 to ·OH conversion, exhibiting excellent antibacterial performance against Staphylococcus aureus. The antibacterial activity was increased by over 2000-fold after catalysis. The CS@Fe-N CDs nanozyme also displayed outstanding peroxidase activity (Vmax/Km = 1.77 × 10−6/s), 8.8-fold higher than horseradish peroxidase. Additionally, the CS@Fe-N CDs nanozyme exhibited high stability at broad pH values (pH 1–12) and temperature ranges (20–90 °C). In vitro evaluation of cell toxicity proved that the CS@Fe-N CDs nanozyme had negligible cytotoxicity. In vivo, wound healing experiments demonstrated that the CS@Fe-N CDs could shorten the healing time of rat wounds by at least 4 days, and even had a better curative effect than penicillin. In conclusion, this therapeutic platform provides an effective antibacterial and biologically safe healing strategy for skin wounds.

MOFs-derived Cu/Carbon membrane as bi-functional catalyst: Improving catalytic activity in detection and degradation of PFOA via regulation of reactive Cu species

Developing bi-functional materials to simultaneously detect and degrade persistent pollutant perfluorooctanoic acid (PFOA) is of significant importance for environmental and human health. In this study, a copper-based mimic enzyme colorimetric detecting sensor coupling with solar photo-electro-Fenton degradation (SPEF) system was built based on Cu/carbon nanofiber (CNF-Cu/C) membrane. Self-supporting flexible CNF-Cu/C membrane was successfully prepared by solvothermal method with further secondary seed growth and in-situ thermal reduction. Based on calcination temperature regulation, the obtained CNF-Cu/C membrane derived from MOFs/polyacrylonitrile (HKUST/PAN) membrane was characterized by 3D carbon fiber network dispersed with porous carbon skeleton embedded copper species, which exhibited good dispersibility, cycling stability and excellent electrical conductivity. With excellent peroxidase-like activity, CNF-Cu/C can rapidly detect PFOA based on the inhibition of color reaction of tetramethylbenzidine (TMB) with detection limit of 0.133 μM. Furthermore, CNF-Cu/C also exhibited outstanding optical properties and oxygen redox reaction (ORR) activity, and the removal efficiency of PFOA in Cu-SPEF system reached 98.22 % within 180 min under optimal conditions. Based on the results of free radical quenching experiment, EPR experiment and HPLC-MS experiments, the degradation mechanism and degradation path of PFOA by SPEF system were further speculated.

One-Step Synthesis of Hollow CoS2 Spheres Derived from Polyoxometalate-Based Metal-Organic Frameworks with Peroxidase-like Activity.

In this work, hollow CoS2 particles were prepared by a one-step sulfurization strategy using polyoxometalate-based metal-organic frameworks as the precursor. The morphology and structure of CoS2 have been monitored by scanning electron microscopy, X-ray photoelectron spectroscopy, and X-ray powder diffraction. The mechanism for the formation of CoS2 is discussed. The reaction time and sulfur content are found to be important factors that affect the morphology and pure phase formation of CoS2, and a hollow semioctahedral morphology of CoS2 with open voids was obtained when the sulfur source was twice as large as the precursor and the reaction time was 24 h. The CoS2 (24 h) particles show an excellent peroxidase-like activity for the oxidation of colorless 3,3',5,5'-tetramethylbenzidine (TMB) to blue oxidized (oxTMB) by hydrogen peroxide. The polyoxometalate used as a precursor helps to stabilize oxTMB during catalytic oxidation, forming a stable curve platform for at least 8 min. Additionally, the colorimetric detection of hydroquinone is developed with a low detection limit of 0.42 μM. This research provides a new strategy to design hollow materials with high peroxidase-mimicking activity.

Phages modified hydrogel pellet assembled in 3D printed both-in-one device for detecting Pseudomonas aeruginosa based on colorimetric and pressure readout modes

Pseudomonas aeruginosa (P. aeruginosa) with noticeable drug-resistance profile is one of the most pernicious pathogens that attracts major public health concerns. Herein, a 3D printed device combined with hydrogel pellet modified with phages was designed for point-of-care testing (POCT) of this pathogen with both colorimetric and pressure readout modes. A P. aeruginosa phage belonging to the family of Podoviridae was isolated from river water and noted as vB_PaeP-JZ1 (JZ1). Due to its host specificity, phage JZ1 was used as a recognizing agent for modifying the hydrogel pellet, and the modified hydrogel pellet was assembled into the 3D printed device to act as the sensing interface. Polymyxin B (PMB) was tagged with Pd@Pt core-shell nanodendrites (Pd@PtNDs) showing excellent peroxidase-like activity to act as the colorimetric and pressure signal tracer. P. aeruginosa can be quantified within the concentration ranges of 2.6 × 103 cfu mL−1 - 2.6 × 108 cfu mL−1 and 2.6 × 102 cfu mL−1 - 2.6 × 107 cfu mL−1 with colorimetric and pressure readout modes, respectively. The both modes can achieve quantitation of P. aeruginosa within 25 min. Thus the “both-in-one” 3D printed device with dual-mode readout function offers a rapid, sensitive, and specific platform for POCT of pathogenic bacteria.

Tungsten-based polyoxometalate nanoclusters with remarkable reactive oxygen species-scavenging activity efficiently quenched luminol-based electrochemiluminescence for sensitive detection of Her-2.

This study aimed to develop a quenching-type electrochemiluminescence (ECL) immunosensor for human epidermal growth factor receptor (Her-2) detection. Firstly, Pd/NiFeOx nanoflowers decorated by in situ formation of gold nanoparticles (Au NPs) and 2D Ti3C2 MXene nanosheets were synthesized (AuPd/NiFeOx/Ti3C2) as carriers to load luminol and primary antibodies. Impressively, AuPd/NiFeOx/Ti3C2 with excellent peroxidase-like activity could accelerate the decomposition of the coreactant H2O2 generating more reactive oxygen species (ROSs) under the working potential from 0 to 0.8V, resulting in highly efficient ECL emission at 435-nm wavelengths. Theintroduction of tungsten-based polyoxometalate nanoclusters (W-POM NCs) which exhibit remarkable ROSs-scavenging activity as secondary antibody labels could improve the sensitivity of immunosensors. TheZnO nanoflowers were employed to encapsulate minute-sized W-POM NCs, and polydopamine was self-polymerized on the surface of Zn(W-POM)O to anchor secondary antibodies. The mechanism of the quenching strategy was explored and it was foundthat W-POM NCs could consume ROSs by the redox reaction of W5+ resulting in W6+. The proposed ECL immunosensor displayed a wide linear response range of 0.1pg·mL-1 to 50ng·mL-1, and a low detection limit of 0.036pgmL-1 (S/N = 3). The recoveries ranged from 93.9 to 99.4%, and the relative standard deviation (RSD) was lower than 10%. This finding is promising for the design of detecting new protein biomarkers.

A versatile CuCo@PDA nanozyme-based aptamer-mediated lateral flow assay for highly sensitive, on-site and dual-readout detection of Aflatoxin B1

Mycotoxin contaminations in food and environment seriously harms human health. Constructing sensitive and point-of-test early-warning tools for mycotoxin determination is in high demand. In this study, a CuCo@PDA nanozyme-based aptamer-mediated lateral flow assay (Apt-LFA) has been elaborately designed for on-site and sensitive determination of mycotoxin Aflatoxin B1 (AFB1). Benefiting from the rich functional groups and excellent peroxidase-like activity, the CuCo@PDA with original dark color can be conjugated with the specific recognition probe (i.e., aptamer), generating colorimetric signal on the test lines of Apt-LFA via a competitive sensing strategy. The signal can further be amplified in-situ by catalytic chromogenic reaction. Therefore, a visual and dual-readout detection of AFB1 has been realized. The developed Apt-LFA provides a flexible detection mode for qualitative and quantitative analysis of AFB1 by naked-eyes observation or smartphone readout. The smartphone-based LFA platform shows a reliable and ultrasensitive determination of AFB1 with the limit of detection (LOD) of 2.2 pg/mL. The recoveries in the real samples are in the range of 95.11–113.77% with coefficients of variations less than 9.84%. This study provides a new approach to realize point-of-test and sensitive detection of mycotoxins in food and environment using nanozyme-based Apt-LFAs.

Edge-generated N-doped carbon-supported dual-metal active sites for enhancing electrochemical immunoassay

Development of high-precision human epidermal growth factor receptor 2 (HER2) assay is essential for the early diagnostic and prevention of breast cancer. In this work, an innovative Fe/Mn bimetallic nanozyme at the edge of N-doped carbon defects (FeMn-NCedge) with abundant active sites was prepared through the hydrothermal synthetic method. FeMn-NCedge nanozyme displayed excellent peroxidase-like activity relative to the H2O2-catalyzed 3,3′,5,5′-tetramethylbenzidine (TMB) system for generation of the oxidized TMB (oxTMB). As a proof-of-concept application, we constructed an electrochemical immunoassay for the detection of HER2 based on the unique merits of FeMn-NCedge. Initially, a sandwiched immunoreaction was carried out in the microtiter plate coated with monoclonal anti-HER2 capture antibodies using glucose oxidase (GOx)-labeled anti-HER2 as detection antibody. The carried GOx could catalyze glucose to produce H2O2, thus resulting in the formation of oxTMB with the assistance of TMB and FeMn-NCedge nanozyme. The produced oxTMB could be determined on the electrode by the chronoamperometry at an applied potential of +10 mV. Experimental results revealed that the steady-state current increased with the increasing HER2 concentration in the sample, and gave a good linear relationship within the dynamic range of 0.01–10 ng/mL at a limit of detection of 5.4 pg/mL HER2. In addition, good reproducibility, high specificity and acceptable accuracy were acquired for the measurement of human serum samples. Importantly, this method can be extended for quantitative monitoring other disease-related proteins by changing the corresponding antibodies.

Cu-Fe nanoparticles decorated rice hull/chitosan@FeAl2O4 to boosted peroxidase-like activity for catalytic degradation of antibiotics: Kinetics and mechanistic insights

A series of derived magnetic porous carbon skeleton-coated Cu/Fe nanocomposites (CunFe1-n@CRH-x) were synthesized using chitosan-rice hull waste-hercynite by an injection molding and impression method, which is introduced as a “treating wastewater by waste residuals” for environmental-friendly remediation. Specifically, the CRH-x is a unique platform for the growth of uniformly dispersed metal oxides with high catalytic performance. After that, the morphological and structural features of post-synthesized nanocomposites were fully identified by applying alternative analytical and spectroscopic tools. The peroxidase-like activity of catalysts via electron transfer process between the simultaneously surface-activated H2O2 and target contaminants (e.g., tetracycline (TC), naproxen (NPX), ciprofloxacin (CIP), and paracetamol (PC)) were evaluated in detail. In the following, to find interrelationships between catalytic performance and structural characteristics, environmental parameters, ions interface, long-term stability, reusability, removal pathway, and universality of the system in various water sources were investigated in detail. The excellent peroxidase-like activity of Cu0.6Fe0.4@CRH-400 can be related to the high Brønsted acid intensity, small pore size, high surface area, and dual-synergy of Cu-Fe nanocatalyst and H2O2. The Cu0.6Fe0.4@CRH-400 can be boosted electron transfer via the dual redox cycle of Cu2+/Cu+/Cu2+ and Fe3+/Fe2+/Fe3+ under its core–shell scaffold, which promoted the generation and/or conversion of active species (•OH2, O2•-) to •OH. 98.20 % of TC, 93.90 % of NPX, 92.10 % of CIP and 100 % of PC were degraded through a rate constant (and TOC (%) removal) of 0.0838 min−1 (51.10 %), 0.0897 min−1 (46.5 %), 0.0737 min−1 (42.30 %), and 0.1168 min−1 (54.6) in Cu0.6Fe0.4 @CRH-400/H2O2 system, respectively, which confirmed that the remediation follows pseudo-1st-order kinetic model. Additionally, the low activation energy of 22.04 kJ/mol and favorable ΔH (−19.60 kJ/mol) of TC degradation confirmed the effectiveness of the catalytic system. Importantly, the reaction pathway was proposed and then predicted the acute toxicity (oral LD50) and mutagenicity of the degradation intermediates. The fairly high degree of mineralization, high anti-interferences, broad-spectrum remediation capacity, adaptability to predominant environmental conditions, and wide pH range (3.0–9.0) by Cu0.6Fe0.4 @CRH-400/H2O2 system in the various real water matrices further endorsed the superiority of the catalytic system.

Reduced graphene oxide-persimmon tannin/Pt@Pd nanozyme-based cascade colorimetric sensor for detection of 1,5-anhydroglucitol.

1,5-anhydroglucitol (1,5-AG) is of considerable clinical relevance as a biochemical marker of glucose metabolism in the assessment and monitoring of diabetes. Herein, a simple colorimetric biosensor was constructed for the identification and detection of 1,5-AG by using pyranose oxidase (PROD) enzyme cascaded with reduced graphene oxide/persimmon tannin/Pt@Pd (RGO-PT/Pt@Pd NPs) nanozyme. The as-prepared RGO-PT/Pt@Pd NPs had excellent peroxidase-like activity and can be applied as a nanozyme. First, PROD enzyme reacts with the target 1,5-AG, decomposing 1,5-AG into 1,5-anhydrofuctose (1,5-AF) and H2O2. At this point, the highly catalytic RGO-PT/Pt@Pd NPs nanozyme produces a cascade with PROD enzyme which catalyzes the decomposition of H2O2 to produce O2. This in turn oxidizes the substrate 3,3',5,5'-tetramethylbenzidine (TMB) and produces a color change in the solution. Finally, the detection of 1,5-AG was achieved by measuring the absorption peak at 652nm with an ultraviolet visible (UV-vis) spectrophotometer. Under optimal conditions, the linear operating range of the 1,5-AG enzyme cascade colorimetric sensor was 1.0-100.0μg/mL, and the limit of detection (LOD) was 0.81μg/mL. The proposed colorimetric biosensor was successfully applied to detect 1,5-AG in spiked human serum samples with the recoveries of 97.2-103.9% and RSDs of 1.94-4.48%. It provides a promising developmental assay for clinical detection of 1,5-AG.

Ru doping enhance the peroxidase-like activity of CeO2 nanorods and application for cysteine determination at physiological temperature

It is an important task that exploring highly active peroxidase-like nanozymes to construct a real-time sensing platform for determining some biomolecules. Among the strategies of active improving of nanozymes, element doping is considered as one of the effective means. In this work, ruthenium (Ru) doping can enhance the peroxidase-like activity of cerium dioxide (CeO2). The peroxidase-like behaviors of Ru-doped CeO2 (Ru/CeO2) are evaluated using the chromogenic substrate 3,3,5,5-tetramethylbenzidine (TMB) and H2O2, respectively. As expected, Ru/CeO2 exhibits more excellent peroxidase-like activity than that of pure CeO2. The improvement of Ru/CeO2 catalytic activity is from the more exposed active sites, due to Ru doping and then defects producing. Furthermore, active species (•O2- and holes h+) were produced during the catalytic reaction. Notably, the catalytic activity of Ru/CeO2 at 37 °C (physiological temperature) still keeps the 95.12% of that at 40 °C, which is important for determination of biological samples. Combining the enhanced peroxidase-like activity of Ru/CeO2 with substrate TMB, a fast facile colorimetric platform for determination of Cysteine (Cys) has been constructed and validated by serum samples.