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Metal–organic frameworks (MOFs) show excellent catalytic activity and have been widely applied in diagnosis of diseases and tumors. However, current assay methods usually involve cumbersome configurations and complicated procedures, which inhibit their practical applications. Hence, a Cu–Ni MOF/carbon printed electrode (CPE)-based integrated electrochemical immunosensor was constructed for highly sensitive and efficient determination of carcinoembryonic antigen (CEA). First, highly conductive carbon ink was screen-printed onto a polyethylene terephthalate substrate to manufacture a CPE. Afterward, an aminated Cu-Ni MOF was prepared by a typical solvothermal strategy and modified on the CPE. Owing to its excellent peroxidase activity, the Cu–Ni MOF can catalytically oxidize hydroquinone using hydrogen peroxide, which greatly amplifies the peak current signal. Then the formation of an immune complex inhibited the catalytic activity of the MOF, thus enabling the quantitative determination of CEA content with a wide linear range of 0.5 pg mL−1–500 ng mL−1 and a low detection limit of 0.16 pg mL−1. Furthermore, the Cu–Ni MOF/CPE-based integrated portable electrochemical immunosensor also showed satisfactory performance in the detection of CEA in clinical serum samples with excellent accuracy, showing great potential for application in point-of-care disease diagnosis. [ABSTRACT FROM AUTHOR]

In this research, dual-strategy biosensing of glucose was proposed based on multifunctional CuWO4 nanoparticles (CuWO4 NPs), which were prepared for the application of electrochemical and colorimetric sensing of glucose. CuWO4 NPs show large specific surface area and good conductivity as well as excellent peroxidase-like activity. A sensitive and selective electrochemical glucose biosensor was fabricated with the immobilization of glucose oxidase (GOx) on a CuWO4 NP modified electrode for enhancing the direct electron transfer behavior. A wide linear range of 0.005–1.8 mM with a low detection limit of 1.5 μM and a high sensitivity of 28.02 mA M−1 cm−2 were achieved by using the electrochemical biosensor. Meanwhile, a colorimetric and visual glucose biosensor was constructed based on the GOx/CuWO4 cascade nanozyme, which shows a linear range of 0.05–1.0 mM with excellent selectivity. CuWO4 NPs as a promising matrix open up a dual-strategy biosensor for sensitive and selective detection of glucose. [ABSTRACT FROM AUTHOR]

The development of flexible substrate materials and nanomaterials with high electrochemical performance is of great significance for constructing efficient wearable electrochemical sensors for real-time health monitoring. Herein, a wearable electrochemical sweat sensor based on a Ni–Co MOF nanosheet coated Au/polydimethylsiloxane (PDMS) film was prepared for continuous monitoring of the glucose level in sweat with high sensitivity. First, a stretchable Au/PDMS film based three-electrode system was prepared by chemical deposition of a gold layer on the hydrophilic treated PDMS. Then, Ni–Co MOF nanosheets with high electrocatalytic activity were synthesized by a facile solvothermal method and modified on the Au/PDMS electrode. The electrocatalytic activity of the Ni–Co MOF nanosheets synthesized under different Ni : Co ratios was investigated. The Ni–Co MOF/Au/PDMS (NCAP) film electrode showed excellent electrochemical performance for glucose detection with a wide linear range of 20 μM to 790 μM and a high sensitivity of 205.1 μA mM−1 cm−2. In addition, the flexible sensor shows high stability and a good electrochemical response to glucose when stretched and bent to different levels. Moreover, it maintained long-term stability and high selectivity for glucose monitoring. Lastly, a sweat-absorbent cloth was used to cover the working area of the sensor and was fixed with a needle and thread to form a wearable sweat glucose sensor. The sensor can be attached to the skin for stable, accurate and continuous monitoring of glucose levels in human sweat for one day. This work validates the potential of our high-performance wearable sensor for out-of-clinic health monitoring. [ABSTRACT FROM AUTHOR]

The poor stability and aqueous-quenching of fluorescence of perovskite nanocrystals (NCs) hinder their application in bio-detection and bio-imaging. Herein, through the synergistic effects of polymer surface ligand and silica encapsulation, highly stable and enhanced aqueous fluorescent CsPbBr3-mPEG@SiO2 NCs were synthesized and used as a novel "on–off–on" fluorescent probe for highly sensitive and selective detection of mercury ions (Hg2+) and glutathione (GSH) in aqueous solutions. The effects of the methoxypolyethylene glycol amine (mPEG-NH2) ligand and silica encapsulation on the stability and aqueous fluorescence of the CsPbBr3 NCs were studied. It indicated that the aqueous fluorescence of perovskite NCs was increased by 2.59 times. The water stability was also greatly improved, with the NCs maintaining 73% of their original fluorescence after storage for 30 days in water. X-ray diffraction (XRD), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FT-IR) analyses further demonstrated that the NCs were successfully passivated by mPEG-NH2 and silica. The fluorescence of the CsPbBr3-mPEG@SiO2 nanocrystals was effectively quenched by Hg2+ which is attributed to the electron transfer process between NCs and Hg2+. Then, through the interaction between Hg2+ and GSH, the restoration of fluorescence for CsPbBr3-mPEG@SiO2 was realized. The "on–off–on" fluorescent probe can be used for the detection of Hg2+ and GSH with a low detection limit of 0.08 nM and 0.19 μM, respectively. It also shows a fast response time and high accuracy for practical sample detection. The simple and sensitive fluorescent probe of CsPbBr3-mPEG@SiO2 shows great potential in environmental and biological sensing. [ABSTRACT FROM AUTHOR]

A covalent organic framework (COF) is a promising type of porous material with customizable surface characteristics. Confining multiple catalytic units within a mesoporous COF can generate abundant active sites and improve the catalytic performance. In this work, a COF with both metalloporphyrin and a metal nanoparticle complex denoted as hemin/TAPB-DMTP-COF/AuNPs (TAPB: 1,3,5-tris(4-amino-phenyl)benzene, DMTP: 2,5-dimethoxyterephaldehyde, AuNPs: Au nanoparticles) has been successfully fabricated through a hierarchical encapsulation method. The as-synthesized composite was then employed to construct an electrochemical sensing platform for the efficient detection of bisphenol A (BPA). Under the optimal conditions, the hemin/TAPB-DMTP-COF/AuNP sensor presented a linear range of 0.01–3 μmol L−1 and a low detection limit of 3.5 nmol L−1. The satisfactory signal amplification is based on a triple-signaling amplification strategy due to the abundant Fe3+ sites of Fe-porphyrin, high conductivity of AuNPs and a large specific surface area of the TAPB-DMTP-COF. The proposed method was used to measure the content of BPA in different water samples with a satisfactory recovery from 95.5 to 104.0%, suggesting the great potential of the sensor in practical applications. [ABSTRACT FROM AUTHOR]

In this research, a novel manganese dioxide nanorod-anchored graphene oxide (MnO2 NRs/GO) composite was synthesized by a simple hydrothermal method for electrochemical sensing application. A highly sensitive electrochemical sensor for dopamine (DA) was constructed by modifying glassy carbon electrode (GCE) with MnO2 NRs/GO. The morphology and performance of the composite material and modified GCEs were investigated by using scanning electron microscopy (SEM), X-ray diffraction (XRD) and cyclic voltammetry (CV), respectively. The resultant MnO2 NRs/GO composite has a large electroactive area and shows excellent electrochemical activity toward DA. Under the optimal conditions, the DA sensor shows a linear response in the DA concentration ranges of 0.1 μM–0.08 mM and 0.08–0.41 mM with a low detection limit of 0.027 μM and a high sensitivity of 602.4 μA·mM−1·cm−2. The MnO2 NRs/GO composite provides a promising platform for the construction of a highly sensitive and selective sensor of DA. [ABSTRACT FROM AUTHOR]

The fabrication of chemically stable metal–organic frameworks for electrochemical sensors is essential to broaden their applications. In this study, the integration of a Zr-based metal–organic framework (UiO-66-NH2) with multi-walled carbon nanotubes (MWCNTs) was achieved by a one-pot solvothermal reaction. This composite was then characterized by scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, Fourier transform infrared spectroscopy, and contact angle measurements. The porous structure and unreacted amine groups provided by UiO-66-NH2 frameworks accompanied by the excellent conductivity of MWCNTs have made this composite an ideal electrode material for lead detection. After the optimization of MWCNT content and the detection conditions, the oxidation peak currents were proportional to lead concentrations in the range of 0.001–0.8 μmol L−1 with a low detection limit of 0.5 nmol L−1 (S/N = 3). More importantly, the well-preserved crystallinity of MWCNTs@UiO-66-NH2 after 80 cycles and after being soaked in different pH aqueous solutions indicates the promising application of this sensor for real samples. Satisfactory recoveries were achieved when this sensor was used to detect lead in real samples. Furthermore, the excellent stability of this composite makes it possible to be employed in other fields, including extreme acidic media. [ABSTRACT FROM AUTHOR]

In this work, a water stable zirconium metal–organic framework functionalized with thiol groups was synthesized by a solvent-assisted ligand incorporation technique. The composites were characterized by powder X-ray diffraction, X-ray photoelectron spectroscopy, specific surface area measurement and field emission scanning electron microscopy. The prepared material was then used as a novel adsorbent for Cu(ii) removal from water. The experimental parameters associated with adsorption capability, such as the initial solution pH, contact time, and the presence of competing cations were investigated in detail. Under the optimal conditions, the adsorption follows a pseudo-second-order kinetics, and the equilibration time for the adsorption is 15 min. The Langmuir adsorption model was in better correlation with the isothermal adsorption data than the Freundlich model. The maximum Cu(ii) adsorption capacity reached up to 42.70 mg g−1. Quantitative recovery of Cu(ii) was achieved by using 0.1 mol L−1 HCl. The prepared adsorbent has fast adsorption efficiency, high adsorption capacity, and exceptional stability up to 50 adsorption/desorption cycles. It can be used as a promising candidate material for heavy metal ion removal and water treatment. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks/titanium dioxide (UiO-66-NH2/TiO2) nanocomposites have been prepared by a simple hydrothermal reaction and they exhibit excellent electrocatalytic activity for chlorogenic acid oxidation due to the synergic effect of UiO-66-NH2 and TiO2. Under the optimal conditions, the sensor can be employed in the quantification of chlorogenic acid in the ranges of 0.01–1.0 μmol L−1 and 1.0–15 μmol L−1 with an ultralow detection limit of 7 nmol L−1 (S/N = 3). Moreover, UiO-66-NH2/TiO2 nanocomposites demonstrate significant stability in acidic buffer solution and maintain their electrocatalytic activities at least up to 90 cycles. The potential utility was validated by the analysis of coffee and tea samples and good recoveries were obtained from different spiked values. The UiO-66-NH2/TiO2 based sensor with highly sensitive, selective and stable consecutive monitoring of chlorogenic acid is a promising candidate for the construction of highly active electrocatalyst in electrochemical biosensors. [ABSTRACT FROM AUTHOR]

In this work, a novel chemically modified electrode is constructed based on metal–organic frameworks and β-cyclodextrin (Cu3(BTC)2/β-CD, BTC = benzene-1,3,5-tricarboxylate) composite material. The electrode was used for simultaneous determination of guanine and adenine in a sequential injection lab-on-valve format and exhibited sensitive responses to guanine and adenine oxidation due to the π–π stacking interaction of Cu3(BTC)2 and the inclusion behavior of β-CD. The analytical performance was assessed with respect to the supporting electrolyte and its pH, accumulation time and accumulation potential, and the fluid flow rates. Under optimal conditions, linear calibration ranges for both guanine and adenine were from 1.0 × 10−7 to 1.0 × 10−5 mol L−1, and detection limits (S/N = 3) were found to be 5.2 × 10−8 and 2.8 × 10−8 mol L−1, respectively. The proposed sensor showed advantages of high sensitivity, simple sample preparation protocol, enhanced throughput and good reproducibility. Finally, the practical application of the proposed sensor has been performed for the determination of guanine and adenine in real samples with satisfactory results. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks have been the subject of intense research because of their unique physicochemical properties. The presented study investigates the application of multi-wall carbon nanotubes and metal–organic frameworks (MWCNTs@Cu3(BTC)2) nanoparticles-modified electrode for the determination of trace levels of lead. The nanocomposites were prepared by solvothermal synthesis and characterized in detail. The experimental procedure was carried out by accumulating lead on the electrode surface and subsequently measuring with differential pulse anodic stripping voltammetry in a lab-on-valve format. The main parameters affecting the analytical performance, including the amount of MWCNTs@Cu3(BTC)2 suspension, supporting electrolyte and its pH, stripping mode, and flow rate, have been investigated in detail. Under the optimum conditions, the oxidation peak current displayed a calibration response for lead over a concentration range from 1.0 × 10−9 to 5.0 × 10−8 mol L−1 with a excellent detection limit of 7.9 × 10−10 mol L−1. The relative standard deviation of 7 successive scans was 3.10% for 1.0 × 10−8 mol L−1 lead. The established method showed a great improvement in sensitivity and sample throughput for lead analysis. [ABSTRACT FROM AUTHOR]

An indirect photoelectrochemical sensing platform for toxic hexavalent chromium was for the first time constructed based on its redox reaction with quercetin as both the electron donor and photosensitizer on a TiO2 photoanode, and thus inhibiting the photocurrent quantitatively and selectively. The presence of even 500-fold coexisting Cr(iii) does not interfere in the detection of Cr(vi). Under the optimum conditions, the electrode displayed a linear decrease response as the Cr(vi) concentration increased from 1 to 10 nmol L−1 and from 20 to 140 nmol L−1 with a detection limit of 0.24 nmol L−1. Many possible ions in drinking water did not interfere with the detection, and the real sample detection results agreed well with those obtained by GFAAS. This work provide a novel methodology for the simple, low-cost photoelectrochemical detection of Cr(vi) in drinking water. [ABSTRACT FROM AUTHOR]

In this research, dual-strategy biosensing of glucose was proposed based on multifunctional CuWO 4 nanoparticles (CuWO 4 NPs), which were prepared for the application of electrochemical and colorimetric sensing of glucose. CuWO 4 NPs show large specific surface area and good conductivity as well as excellent peroxidase-like activity. A sensitive and selective electrochemical glucose biosensor was fabricated with the immobilization of glucose oxidase (GOx) on a CuWO 4 NP modified electrode for enhancing the direct electron transfer behavior. A wide linear range of 0.005-1.8 mM with a low detection limit of 1.5 μM and a high sensitivity of 28.02 mA M -1 cm -2 were achieved by using the electrochemical biosensor. Meanwhile, a colorimetric and visual glucose biosensor was constructed based on the GOx/CuWO 4 cascade nanozyme, which shows a linear range of 0.05-1.0 mM with excellent selectivity. CuWO 4 NPs as a promising matrix open up a dual-strategy biosensor for sensitive and selective detection of glucose.

The poor stability and aqueous-quenching of fluorescence of perovskite nanocrystals (NCs) hinder their application in bio-detection and bio-imaging. Herein, through the synergistic effects of polymer surface ligand and silica encapsulation, highly stable and enhanced aqueous fluorescent CsPbBr 3 -mPEG@SiO 2 NCs were synthesized and used as a novel "on-off-on" fluorescent probe for highly sensitive and selective detection of mercury ions (Hg 2+ ) and glutathione (GSH) in aqueous solutions. The effects of the methoxypolyethylene glycol amine (mPEG-NH 2 ) ligand and silica encapsulation on the stability and aqueous fluorescence of the CsPbBr 3 NCs were studied. It indicated that the aqueous fluorescence of perovskite NCs was increased by 2.59 times. The water stability was also greatly improved, with the NCs maintaining 73% of their original fluorescence after storage for 30 days in water. X-ray diffraction (XRD), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FT-IR) analyses further demonstrated that the NCs were successfully passivated by mPEG-NH 2 and silica. The fluorescence of the CsPbBr 3 -mPEG@SiO 2 nanocrystals was effectively quenched by Hg 2+ which is attributed to the electron transfer process between NCs and Hg 2+ . Then, through the interaction between Hg 2+ and GSH, the restoration of fluorescence for CsPbBr 3 -mPEG@SiO 2 was realized. The "on-off-on" fluorescent probe can be used for the detection of Hg 2+ and GSH with a low detection limit of 0.08 nM and 0.19 μM, respectively. It also shows a fast response time and high accuracy for practical sample detection. The simple and sensitive fluorescent probe of CsPbBr 3 -mPEG@SiO 2 shows great potential in environmental and biological sensing.

Co(3)O(4) nanoparticles (NPs) with an average diameter of about 20 nm were synthesized by using MOFs as a template. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to characterize the as-prepared Co(3)O(4) NPs. Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) were used to confirm the structure of the Co(3)O(4) NPs. Then the Co(3)O(4) NPs were modified on a glassy carbon electrode (GCE) to obtain a non-enzymatic glucose and H(2)O(2) sensor. The NPs show electrocatalytic activity toward oxidation of glucose and H(2)O(2) in alkaline medium. For glucose detection, the developed sensor shows a short response time (less than 6 s), a high sensitivity of 520.7 μA mM(-1) cm(-2), a detection limit of 0.13 μM (S/N = 3), and good selectivity. The high concentration of NaCl does not poison the electrode. Its application for the detection of glucose in a human blood serum sample shows good agreement with the results obtained from the hospital. Furthermore, the proposed sensor was used for the detection of H(2)O(2). The results indicate that the detection limit and sensitivity for H(2)O(2) are 0.81 μM and 107.4 μA mM(-1) cm(-2), respectively. Determination of H(2)O(2) concentration in a disinfectant sample by the proposed biosensor also showed satisfactory result. The high sensitivity and low detection limit can be attributed to the excellent electrocatalytic performance of the as-prepared Co(3)O(4) NPs. These results demonstrate that the as-prepared Co(3)O(4) NPs have great potential applications in the development of sensors for enzyme-free detection of glucose and H(2)O(2).

In this study, an automated sequential injection lab-on-valve (SI-LOV) system was designed for the on-line matrix removal and preconcentration of quercetin. Octadecyl functionalized magnetic silica nanoparticles were prepared and packed into the microcolumn of the LOV as adsorbents. After being adsorbed through hydrophobic interaction, the analyte was eluted and subsequently introduced into the electrochemical flow cell by voltammetric quantification. The main parameters affecting the performance of solid-phase extraction, such as sample pH and flow rate, eluent solution and volume, accumulation potential and accumulation time were investigated in detail. Under the optimum experimental conditions, a linear calibration curve was obtained in the range of 1.0 × 10(-8) to 1 × 10(-5) mol L(-1) with R(2) = 0.9979. The limit of detection (LOD) and limit of quantitation (LOQ) were 1.3 × 10(-9) and 4.3 × 10(-9) mol L(-1), respectively. The relative standard deviation (RSD) for the determination of 1.0 × 10(-6) mol L(-1) quercetin was found to be 2.9% (n = 11) along with a sampling frequency of 40 h(-1). The applicability and reliability of the automated method described here had been applied to the determination of quercetin in human urine and red wine samples through recovery experiments, and the obtained results were in good agreement with those obtained by the HPLC method.

The miniaturized lab-on-valve (LOV) manifold well hyphenated with indirect biamperometry is presented for automated determination of trace level concentrations of organic environmental pollutants by programmable flow. The experimental procedure was carried out by means of taking o-phenylenediamine (OPDA) as a model analyte, relying on the Fe(iii)/Fe(ii) couple that served as an indicating redox system. The miniaturized electrochemical flow cell (EFC) designed and processed was integrated into the LOV module which is assembled with two identical polarized platinum electrodes between which a small potential difference (ΔE) was applied, to implement automated on-line analysis in a closed system. Factors affecting analytical performance are discussed, including indicating redox systems, concentration of indicating system, the acidity, the potential difference, and flow variables in the LOV. The calibration curve showed an excellent linearity in the concentration range of 5.0 × 10(-7) to 1.0 × 10(-4) mol L(-1) (R(2) = 0.9993). The limits of detection (LOD) and quantitation (LOQ) for OPDA were found to be 1.1 × 10(-7) and 3.7 × 10(-7) mol L(-1), respectively. A sampling frequency of 40 h(-1) was obtained along with an R.S.D. of 2.8% at 1.0 × 10(-6) mol L(-1) OPDA (n = 11). The proposed procedure was successfully applied to the assay of OPDA in industrial waste water.