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.

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.

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.

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.

Glow-type luminol chemiluminescence based on a supramolecular enhancer of cyclodextrin.

BACKGROUND: Chemiluminescence (CL) bioassay is one of the most advanced and used detection method in clinical diagnosis and biomedical research because of the advantages of low background, easy operation, and wide-field imaging without a light source or microscope. The luminol/hydrogen peroxide/horseradish peroxidase (luminol/H2O2/HRP) system is the most popular CL system, but its application in high-throughput imaging detection is challenged due to its low luminescence efficiency and flash-type emission which is difficult in ensuring the reproducibility and consistency of detection results. RESULTS: We reported a glow-type CL system of luminol@CD/H2O2/HRP by using a supramolecular enhancer of cyclodextrin (CD). This luminol@CD/H2O2/HRP system exhibited a luminescence lifetime of 41 min for sensitive and accurate imaging analysis. The long-lasting CL emission was attributed to the formation of a 1:1 host-guest complex between luminol and CD, which could stabilize the emitter and effectively reduce nonradiative relaxation. The formation of luminol@CD complex was determined through NMR experiments and theoretical analysis. Under optimum conditions, the luminol@CD/H2O2/HRP system showed higher sensitivity and much better precision than classical luminol/H2O2/HRP system for imaging detection of HRP. Especially, this glow-type luminol@CD/H2O2/HRP system realized CL imaging of microwell arrays on microfluidic chips. In addition, the luminol@CD/H2O2/HRP system was successfully applied for point-of-care detection of 17ß-estradiol based on a competitive mechanism of host-guest recognition. SIGNIFICANCE: An efficient CL system is crucial for obtaining reproducible and consistent results for accurate detection. Our luminol@CD/H2O2/HRP system emitted strong and persistent luminescence, resulting in reliability and efficiency at both CL macroscopic and microscopic imaging detection. We expected the luminol@CD/H2O2/HRP CL system to be applied in various detection fields.

A fluorimetric and colorimetric dual-mode sensor based on N, S co-doped carbon dots functionalized silver nanoparticles for glucose detection.

A fluorescent-colorimetric dual-signal platform, N, S co-doped carbon dots functionalized silver nanoparticles (NS-CDs-AgNPs), was designed in situ by reducing AgNO3 in the presence of N, S co-doped carbon dots (NS-CDs) under the assistance of microwave irradiation for glucose determination. With the formation of silver nanoparticles (AgNPs), the intrinsic fluorescence of NS-CDs was quenched, showing the fluorescence state was off. Whereas the fluorescence of NS-CDs can be switched on when a trace amount of H2O2 was added. Based on this novel phenomenon, the peroxidase-like activity of NS-CDs-AgNPs by using 3,3',5,5'-tetramethylbenzidine (TMB) chromogen and H2O2 as substrates was evaluated. The Km values of the prepared probe for H2O2 and TMB were 0.84 mM and 0.01 mM with the Vm of 6.65 × 10-8 M S-1 and 3.01 × 10-8 M S-1, respectively. The results showed that NS-CDs-AgNPs had good peroxidase-like activity and strong affinity to TMB and H2O2. It confirmed that there is a redox interaction between AgNPs and H2O2, and H2O2 can oxidize Ag to produce Ag+, which is the main reason that the fluorescence of NS-CDs-AgNPs can be activated by H2O2. The hydroxyl radical (·OH) was formed in the process of reaction, which can further oxidize TMB for color reaction. Meanwhile, glucose can be oxidized to produce H2O2 in the presence of glucose oxidase (GOx). Based on the phenomenon, a fluorimetric and colorimetric dual-mode sensor for glucose detection was established. Satisfactory results were obtained with the linear range of 0.1-80 µM for fluorimetric mode and 0.5-5 µM for colorimetric mode, respectively. Additionally, the LOD was below 0.32 µM and 0.21 µM, respectively. The method was successfully applied to determine the glucose in human serum with satisfactory recovery and RSD.

Bimetallic Single-Atom Nanozyme-Based Electrochemical-Photothermal Dual-Function Portable Immunoassay with Smartphone Imaging.

Rapid and accurate detection of human epidermal growth factor receptor 2 (HER2) is crucial for the early diagnosis and prognosis of breast cancer. In this study, we reported an iron-manganese ion N-doped carbon single-atom catalyst (FeMn-NCetch/SAC) bimetallic peroxidase mimetic enzyme with abundant active sites etched by H2O2 and further demonstrated unique advantages of single-atom bimetallic nanozymes in generating hydroxyl radicals by density functional theory (DFT) calculations. As a proof of concept, a portable device-dependent electrochemical-photothermal bifunctional immunoassay detection platform was designed to achieve reliable detection of HER2. In the enzyme-linked reaction, H2O2 was generated by substrate catalysis via secondary antibody-labeled glucose oxidase (GOx), while FeMn-NCetch/SAC nanozymes catalyzed the decomposition of H2O2 to form OH*, which catalyzed the conversion of 3,3',5,5'-tetramethylbenzidine (TMB) to ox-TMB. The ox-TMB generation was converted from the colorimetric signals to electrical and photothermal signals by applied potential and laser irradiation, which could be employed for the quantitative detection of HER2. With the help of this bifunctional detection technology, HER2 was accurately detected in two ways: photothermally, with a linear scope of 0.01 to 2.0 ng mL-1 and a limit of detection (LOD) of 7.5 pg mL-1, and electrochemically, with a linear scope of 0.01 to 10 ng mL-1 at an LOD of 3.9 pg mL-1. By successfully avoiding environmental impacts, the bifunctional-based immunosensing strategy offers strong support for accurate clinical detection.

Controllable Preparation of a Cu NCs@Zn-MOF Hybrid with Dual Emission Induced by an Ion Exchange Strategy for the Detection of Explosives.

The precise synthesis of Cu NCs is a highly desirable and controllable route for the preparation of desired structures and properties, which facilitates the rational design of valuable probes for fluorescence sensing and the understanding of structure-property relationships. Herein, an ion-exchange strategy combined with a bottom-up synthetic approach was utilized in the synthesis process of Cu NCs for the first time, which achieved the controllable synthesis of Cu NCs and in situ anchoring of Cu NCs on the support material HPU-14. The as-prepared Cu NCs@HPU-14-4h not only had a good peroxidase-like property but also exhibited stable dual-emitting fluorescence at 470 and 620 nm. Notably, the peroxidase-like property endowed Cu NCs@HPU-14-4h with the capability of highly sensitive colorimetric detection of H2O2 in a linear concentration from 0.1 to 140 µM (detection limit of 86.7 nM), and a change in the fluorescent color from red to blue could be observed by the naked eye. Furthermore, due to the large overlap between the absorption of 2,4,6-trinitrophenol (TNP) and the excitation band of Cu NCs@HPU-14-4h, TNP could also be detected from 27 types of analogs and common ions with a limit of detection of 68 nM. Finally, a portable hydrogel probe with efficient wipe sampling was fabricated by polyvinyl alcohol (PVA) comprising Cu NCs@HPU-14-4h with the aim of on-site visualization of different explosives. Consequently, the current study not only provides a new idea for the precise synthesis of Cu NCs and their controllable anchoring on support materials but also offers an effective method for predicting H2O2 and TNP.

A noble metal-enhanced Au@CuO heterostructure with multienzyme-mimicking activities for colorimetric detection of tannic acid.

Nanozymes, serving as synthetic alternatives to natural enzymes, offer several benefits including cost-effectiveness, enzyme-like catalytic abilities, enhanced stability, adjustable catalytic activity, easy recyclability, mild reaction conditions, and environmental friendliness. Nonetheless, the ongoing quest to develop nanozymes with enhanced activity and to delve into the catalytic mechanism remains a challenge. In our research, we effectively developed Au@CuO nanocomposites (Au@CuO Nc), replicating the functions of four enzymes found in nature: peroxidase (POD), catalase (CAT), glutathione peroxidase (GPx), and oxidase (OXD). The catalytic efficiency of Au@CuO Nc for TMB oxidation (oxTMB) was approximately 4.8 times greater than that of plain Cu2O cubes, attributed to the synergistic catalytic impact between the Au element and Cu2O within Au@CuO Nc. Mechanistic studies revealed that the novel Au@CuO Nc nanozyme greatly enhances the decomposition of H2O2 to reactive oxygen species (ROS) intermediates (˙OH, ˙O2- and 1O2), resulting in increased POD-like activity of the single-component Cu2O cubes. When an antioxidant like TA was added to the chromogenic system, it converted oxTMB into a colorless form of TMB, enabling further evaluation of TA. Hence, a colorimetric sensor was developed for the rapid and precise quantitative measurement of TA, demonstrating strong linearity between 0.3 and 2.4 µM and featuring a low detection threshold of 0.25 µM. Moreover, this sensor was effectively utilized for the assessment of TA in actual tea samples. This work innovatively proposes a simplified and reliable strategy for the advanced design of highly effective Cu-based nanozymes, enhancing enzyme-like reactions for simultaneous, on-site colorimetric probing of antioxidants.

Bimetal loaded graphitic carbon nitride with synergistic enhanced peroxidase-like activity for colorimetric detection of p-phenylenediamine.

In recent years, great progress has been made on the study of nanozymes with enzyme-like properties. Here, bimetallic Fe and Ni nanoclusters were anchored on the nanosheets of nitrogen-rich layered graphitic carbon nitride by one-step pyrolysis at high temperature (Fe/Ni-CN). The loading content of Fe and Ni on Fe/Ni-CN is as high as 8.0%, and Fe/Ni-CN has a high specific surface area of 121.86 m2 g-1. The Fe/Ni-CN can effectively oxidize 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H2O2, and exhibits efficient peroxidase-like activity, leading to a 17.2-fold increase compared to pure graphitic carbon nitride (CN). Similar to the natural horseradish peroxidase (HRP), the Fe/Ni-CN nanozyme follows catalytic kinetics. The Michaelis-Menten constant (Km) value of the Fe/Ni-CN nanozyme for TMB is about 8.3-fold lower than that for HRP, which means that the Fe/Ni-CN nanozyme has better affinity for TMB. In addition, the catalytic mechanism was investigated by combination of free radical quenching experiments and density-functional theory (DFT) calculations. The results show that the high peroxidase-like activity is due to the easy adsorption of H2O2 after bimetal loading, which is conducive to the production of hydroxyl radicals. Based on the extraordinary peroxidase-like activity, the colorimetric detection of p-phenylenediamine (PPD) was constructed with a wide linear range of 0.2-30 µM and a low detection limit of 0.02 µM. The sensor system has been successfully applied to the detection of residual PPD in real dyed hair samples. The results show that the colorimetric method is sensitive, highly selective and accurate. This study provides a new idea for the efficient enhancement of nanozyme activity and effective detection of PPD by a bimetallic synergistic strategy.

Molecularly imprinted polymer-based electrochemical sensor for rapid detection of masked deoxynivalenol with Mn-doped CeO2 nanozyme as signal amplifier.

Deoxynivalenol-3-glucoside (D3G), the masked form of the important mycotoxin deoxynivalenol (DON), displays potential toxicity but is difficult to control owing to the lack of rapid detection methods. Herein, an innovative molecularly imprinted polymer (MIP)-based electrochemical sensor was developed for the rapid detection of D3G. MIP, an efficient recognition element for D3G, was electropolymerized using o-phenylenediamine based on a surface functional monomer-directing strategy for the first time. CeO2, which contains both Ce3+ and Ce4+ oxidation states, was introduced as a nanozyme to catalyze H2O2 reduction, while Mn doping generated more oxygen vacancies and considerably improved the catalytic activity. Mn-CeO2 also served as a promising substrate material because of its large surface area and excellent conductivity. Under optimal conditions, a good linear relationship was observed for D3G detection over the concentration range of 0.01-50 ng/mL. The proposed sensor could detect D3G down to 0.003 ng/mL with excellent selectivity, even distinguishing its precursor DON in complex samples. The sensor exhibited acceptable stability with high reproducibility and accuracy, and could successfully determine D3G in grain samples. To the best of our knowledge, this is the first electrochemical sensing platform for rapid D3G detection that can easily be expanded to other masked mycotoxins.

Generating luminescent Graphene quantum Dots from Tryptophan: Fluorosensors for hydrogen peroxide in cancer cells.

Herein, we report a single step synthesis of highly fluorescent Graphene Quantum Dots (GQDs) using tryptophan and glycerol as precursors via pyrolysis. The morphological and functional characterization of the prepared GQDs was performed using PXRD, FTIR, TEM, XPS and zeta potential measurements. The prepared GQDs found their practical application in ultrasensitive detection of an emerging potential cancer biomarker, H2O2, by exploiting the fluorescence quenching behaviour of H2O2. To evaluate the detection sensitivity, a series of various concentrations of H2O2 was spiked to biomatrices like, serum and MCF-7 (human breast cancer cell line) cell lysate medium. A remarkably low limit of detection (LOD) was found in serum medium (139.5 pM) which further improved in MCF-7 cell lysate medium (LOD 61.43 pM). Moreover, the sensing capacity of the GQDs was further validated in presence of various physiological variables such as glucose, cholesterol, insulin and nitrite. Sensing assay was also carried out in HaCaT (human keratinocyte cell line) cell lysate medium to compare the performance of our prepared sensor but the non-linearity of the F0/F versus H2O2 concentration plot pointed towards the conduciveness of the MCF-7 cell lysate medium for sensitive detection of H2O2.The mechanism behind the sensing was also explored using spectroscopic methods.

Solid-Phase Electrochemiluminescence Enzyme Electrodes Based on Nanocage Arrays for Highly Sensitive Detection of Cholesterol.

The convenient and sensitive detection of metabolites is of great significance for understanding human health status and drug development. Solid-phase electrochemiluminescence (ECL) enzyme electrodes show great potential in metabolite detection based on the enzyme-catalyzed reaction product hydrogen peroxide (H2O2). Herein, a solid-phase ECL enzyme sensor was fabricated based on a confined emitter and an immobilized enzyme using electrostatic nanocage array, constructing a platform for the sensitive detection of cholesterol. The electrostatic cage nanochannel consists of a bipolar and bilayer vertically aligned mesoporous silica film (bp-VMSF). The upper layer of bp-VMSF is an amino-modified, positively charged VMSF (p-VMSF), and the lower layer is a negatively charged VMSF (n-VMSF). The most commonly used ECL probe tris(bipyridine)ruthenium(II) (Ru(bpy)32+) is fixed in n-VMSF by electrostatic adsorption from n-VMSF and electrostatic repulsion from the upper p-VMSF, generating significantly enhanced and stable ECL signals. The successful preparation of the electrostatic cage was characterized by scanning electron microscopy (SEM) and electrochemical methods. After amino groups on the outer surface of bp-VMSF were derivatized with aldehyde, cholesterol oxidase (ChOx) molecules were covalently immobilized. The successful construction of the enzyme electrode was characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). When the corresponding enzyme substrate, cholesterol, was present in the solution, the ECL signal of Ru(bpy)32+ was quenched by the enzyme-catalyzed reaction product H2O2, enabling the high-sensitivity detection of cholesterol. The linear range for detecting cholesterol was from 0.05 mM to 5.0 mM, with a limit of detection (LOD) of 1.5 µM.

IMSIS: An instrumented microphysiological system with integrated sensors for monitoring cellular metabolic activities.

Well plates are widely used in biological experiments, particularly in pharmaceutical sciences and cell biology. Its popularity stems from its versatility to support a variety of fluorescent markers for high throughput monitoring of cellular activities. However, using fluorescent markers in traditional well plates has its own challenges, namely, they can be potentially toxic to cells, and thus, may perturb their biological functions; and it is difficult to monitor multiple analytes concurrently and in real-time inside each well. This paper presents a fully instrumented microphysiological system with integrated sensors (IMSIS) with a similar well format. Each well in the microphysiological system has a set of sensors for monitoring multiple metabolic analytes in real-time. The IMSIS platform is supported by integrated bioelectronic circuits and a graphical user interface for easy user configuration and monitoring. The system has integrated microfluidics to maintain its microphysiological environment within each well. The IMSIS platform currently incorporates O2, H2O2, and pH sensors inside each well, allowing up to six wells to perform concurrent measurements in real-time. Furthermore, the architecture is scalable to achieve an even higher level of throughput. The miniaturized design ensures portability, suitable for small offices and field applications. The IMSIS platform was successfully used to monitor in real-time the mitochondrial functions of live bovine embryos in O2 consumption, H2O2 release as an indication of ROS production, and extracellular acidity changes before and after the introduction of external substrates.

Breathable Wearable Smartsensors Deriving from Interface Self-Assembled Film for Tracking l-Cysteine.

The advent of wearable sensors heralds a transformation in the continuous, noninvasive analysis of biomarkers critical for disease diagnosis and fitness management. Yet, their advancement is hindered by the functional challenges affiliated with their active sensing analysis layer. Predominantly due to suboptimal intrinsic material properties and inconsistent dispersion leading to aggregation, thus compromising sensor repeatability and performance. Herein, an innovative approach to the functionalization of wearable electrochemical sensors was introduced, specifically addressing these limitations. The method involves a proton-induced self-assembly technique at the organic-water (O/W) interface, facilitating the generation of biomarker-responsive films. This research offers flexible, breathable sensor capable of real-time precision tracking l-cysteine (l-Cys) precision tracking. Utilizing an activation mechanism for Prussian blue nanoparticles by hydrogen peroxide, the catalytic core exhibits a specific response to l-Cys. The implications of this study refine the fabrication of film-based analysis electrodes for wearable sensing applications and the broader utilization of two-dimensional materials in functional-specific response films. Findings illuminate the feasibility of this novel strategy for precise biomarker tracking and extend to pave the way for constructing high-performance electrocatalytic analytical interfaces.

A Three-Dimensional Electrochemiluminescence Sensor Integrated with Peptide Hydrogel for Detection of H2O2 Released from Different Subtypes of Breast Cancer Cells.

Breast cancer is a malignant tumor, with various subtypes showing different behaviors. Endogenous H2O2 is an important marker of tumor progression, which makes it important to study the relationship between breast cancer subtypes and H2O2 for pathogenesis and treatment strategies, but this has rarely been reported so far. In this work, we constructed a three-dimensional (3D) electrochemiluminescence (ECL) sensing platform for the detection of H2O2 released from two typical subtypes of breast cancer cells (MCF-7 cells for luminal A-type and MDA-MB-231 cells for three negative breast cancers, TNBCs). To adequately replicate the tumor microenvironment, the peptide hydrogel was introduced as a scaffold for 3D cell culture. The titanium foam (TF) was used as a 3D electrode to better match the 3D culture substrate. N-(4-Aminobutyl)-N-ethylisoluminol (ABEI) was selected as the ECL emitter and assembled into the peptide hydrogel by hydrogen bonding and π-stacking, which resulted in a stable and homogeneous distribution of ABEI along the hydrogel fibers. Furthermore, basic amino acids were introduced to provide alkaline microenvironment for ABEI. Therefore, ABEI exhibited high ECL efficiency, resulting in a high sensitivity with an ultralow detection limit of 0.023 nM (S/N = 3) for H2O2 of the proposed ECL biosensor. MCF-7 and MDA-MB-231 cells were cultured in a 3D peptide hydrogel/ABEI/TF electrode, respectively, and endogenous H2O2 was successfully monitored. A notably significant difference of H2O2 released between MDA-MB-231 cells and MCF-7 cells without stimulation but similar extra release with stimulation were observed. These findings may help understand the physiological mechanisms behind the various subtypes and reactive oxygen species (ROS)-related treatment for breast cancer.

Colorimetric sensors constructed with one dimensional PtNi nanowire and Pt nanowire nanozymes for Hg2+ detection.

BACKGROUND: In recent years, environmental pollution has attracted widespread global attention. Among them, environmental problems caused by heavy metal pollution pose a serious threat to human health and ecosystems. Mercury is a common heavy metal pollutant with high toxicity and wide distribution. Excessive intake of Hg2+ can cause permanent and severe damage to the nervous system, respiratory system, and kidneys in the human body. Therefore, developing both accurate and fast detection methods for Hg2+ is of great significance. RESULTS: A sensitive Hg2+ colorimetric sensor is designed based on PtNi nanowires (NWs) and Pt NWs with peroxidase-mimetic activity. PtNi NWs and Pt NWs catalyze the reaction of 3,3', 5,5'-tetramethylbenzidine (TMB) with hydrogen peroxide (H2O2) to produce blue oxidized TMB (oxTMB). The specific interaction of Pt-Hg significantly inhibits the peroxidase-mimetic activity of PtNi NW and Pt NW nanozymes, resulting in a lighter blue color. It is worth noting that compared with specific activity (SA) of Pt NWs (3.31 U/mg), PtNi NWs own superior SA (10.43 U/mg), which inevitably leads to a wider linear range of Hg2+ analysis (1 nM-200 µM) and a lower detection limit (0.6748 nM) for PtNi NWs-based colorimetric sensor, versus linear range (4 nM-5 µM) and LOD of 1.198 nM for Pt NWs-based colorimetric sensor, which are far below the Hg2+ threshold (10 nM) for drinking water set by the US Environmental Protection Agency. SIGNIFICANCE: The two nanozyme colorimetric sensors have been successfully used for the evaluation of Hg2+ in complex river water and tap water. Due to the advantages of simple operation, fast response, and high sensitivity, colorimetric sensors have broad application prospects in environmental monitoring.

Monodispersed Au nanoparticles decorated MoS2 nanosheets with enhanced peroxidase-like activity based electrochemical H2O2 sensing for anticancer drug evaluations.

BACKGROUND: The unique size, physical and chemical properties, and ultra-high stability of nanozymes have attracted extensive attentions in sensing, but improvement of catalytic activity of the nanozymes is still an urgent issue. Given the ultra-high simulated enzyme activity of metal nanoparticles and the advantage of multi-enzyme catalysis, an Au-decorated MoS2 nanosheets (MoS2/Au NS) integrating the double peroxidase-like (POD) activity is developed. RESULTS: By optimizing and adjusting the density of AuNPs, as well as its morphology and other parameters, a monodisperse and high-density distribution of AuNPs on MoS2 nanosheets was obtained, which can greatly improve the POD-like activity of MoS2/Au NS. Nafion solution was applied to assist the modification of MoS2/Au NS on the electrode surface so as to improved its stability. An electrochemical H2O2 detection platform was constructed by modifying MoS2/Au NS nanozyme on the SPCE using the conductive Nafion solution. And the negatively charged sulfonic acid group can eliminate negatively charged electroactive substances to improve the specificity. Then ascorbic acid was used to stimulate tumor cells to produce H2O2 as therapeutic model, an ultrasensitive chronocoulometry detection for H2O2 in cell lysate was established. The logarithmically of ΔQ and the logarithmically of H2O2 concentration showed a good linear relationship between 1 µM and 500 mM, with a LOD value of 0.3 µM. SIGNIFICANCE: The developed H2O2 sensor has excellent stability, reproducibility (RSD = 2.3 %, n = 6) and selectivity, realized the quantitative detection of H2O2 in cell lysate. Compared with commercial fluorescence detection kits for H2O2 in cell lysate, it is worth mentioning that the electrochemical H2O2 sensor developed in this study is simpler and faster, with higher sensitivity and lower cost. This provides a potential substitute for disease diagnosis and treatment evaluation based on accurate detection of H2O2.

A colorimetric platform for sensitive sensing of Hg2+ and S2- based on Se-AuNPs with Hg2+-activated peroxidase-like activity.

Herein, the selenium (Se) modified gold nanoparticles (Se-AuNPs) was synthesized using cerium doped carbon dots (Ce-CDs) as a reducing agent and template. As desired, Se-AuNPs displays enhanced peroxidase (POD)-like activity in the presence of Hg2+. The mechanism for the enhanced activity was attributed to the increased affinity between Se-AuNPs-Hg2+ and the substrate, in which Se and Au elements have a strong binding capacity to Hg2+, forming Hg-Se bonds and Au-Hg amalgam to generate more ·OH. This POD-like activity of Se-AuNPs-Hg2+ correlates with the colorimetric reaction by the catalytic reaction between 3,3',5,5'-tetramethylbenzidine (TMB) and H2O2. The oxidation of TMB was completely inhibited by the introduction of the reductive S2-. Based on the above findings, a strategy for the colorimetric detection of Hg2+ and S2- by Se-AuNPs was established with linear ranges of 0.33-66 µg/L and 0.625-75 µg/L, and low detection limits of 0.17 µg/L and 0.12 µg/L (3.3 δ/k), respectively. When the colorimetric probes for detection of Hg2+ and S2- was applied in environmental water samples, the recoveries were in the range of 90.3-108.0 %. This method will provide a new idea for the colorimetric detection strategy of Hg2+ due to the strong interaction between Hg and Se.

Engineering the nanozyme hydrogel beads by polyvinyl alcohol/chitosan encapsulation with recyclable and sustainable catalytic activity for visual analysis of hydrogen peroxide.

BACKGROUND: Hydrogen peroxide (H2O2) plays a vital role in human health and have been regarded as a crucial analyte in metabolic processes, redox transformations, foods research and medical fields. Especially, the long-time and excessive digestion of H2O2 may even cause severe diseases. Although conventional instrumental methods and nanozymes-based colorimetric methods have been developed to accomplish the quantitative analysis of H2O2, the drawbacks of instrument dependence, cost-effectiveness, short lifespan, non-portable and unsustainable detection efficacies will limit their applications in different detection scenarios. RESULTS: Herein, to address these challenges, we have proposed a novel strategy for nanozyme (RuO2) hydrogel preparation by the solid support from cross-linked polyvinyl alcohol (PVA) and chitosan (CS) to both inherit the dominant peroxidase-like (POD) activity and protect the RuO2 from losing efficacies. Taking advantages from the hydrogel, the encapsulated RuO2 were further prepared as the regularly spherical beads (PCRO) to exhibit the sustainable, recyclable, and robust catalysis. Moreover, the intrinsic color interferences which originated from RuO2 can be avoided by the encapsulation strategy to promote the detection accuracy. Meanwhile, the high mechanical strength of PCRO shows the high stability, reproducibility, and cyclic catalysis to achieve the recyclable detection performance and long lifetime storage (40 days), which enables the sensitively detection of H2O2 with the detection limit as lower to 15 µM and the wide detection linear range from 0.025 to 1.0 mM. SIGNIFICANCE: On the basis of the unique properties, PCRO has been further adopted to construct a smartphone detection platform to realize the instrument-free and visual analysis of H2O2 in multi-types of milk and real water samples through capturing, processing, and analyzing the RGB values from the colorimetric photographs. Therefore, PCRO with the advanced detection efficacies holds the great potential in achieving the portable and on-site analysis of targets-of-interest.