Fabrication of a non-enzymatic glucose sensor field-effect transistor based on vertically-oriented ZnO nanorods modified with Fe2O3

Herein, we report a non-enzymatic glucose sensor field-effect transistor (FET) based on vertically-oriented zinc oxide nanorods modified with iron oxide (Fe₂O₃-ZNRs). Compared with ZnO-based non-enzymatic glucose sensors, which show poor sensing performances, modification of ZnO with Fe₂O₃ dramatically enhances the sensing behavior of the fabricated non-enzymatic FET glucose sensor due to the excellent electrocatalytic nature of Fe₂O₃. The fabricated non-enzymatic FET sensor showed excellent catalytic activity for glucose detection under optimized conditions with a linear range up to 18 mM, detection limits down to ~ 12 μM, excellent selectivity, good reproducibility and long-term stability. Moreover, the fabricated FET sensor detected glucose in freshly drawn mouse whole blood and serum samples. The developed FET sensor has practical applications in real samples and the solution-based synthesis process is cost effective.     

Copper Nanoflowers on Carbon Cloth as a Flexible Electrode Toward Both Enzymeless Electrocatalytic Glucose and H2O2

Herein, a novel electrochemical sensor for glucose and hydrogen peroxide (H₂O₂) detection was successfully developed through the use of Cu nanoflowers (CuNFs) combined with flexible carbon cloth (CC) substrate. The 3D flower-like CuNFs in size uniformly and firmly grow on CC substrate by a facile, scalable, one-step hydrothermal strategy. Morphology, size and surface property of the prepared CuNFs/CC were examined by SEM, EDS and TEM, respectively. The electrochemical mechanism of CuNFs/CC for glucose and H₂O₂ detection was investigated by cyclic voltammetry. High electrochemical performances were displayed with amperometric i-t curves including a wide linear range from 1.0 nM to 6.0 mM for glucose and from 1.0 μM to 36.66 mM for H₂O₂, respectively. Good sensitivity, repeatability, and stability, as well as anti-interference ability, the carbon cloth-supported CuNFs will be the promising materials for fabricating practical non-enzymatic glucose and H₂O₂ sensors.     

Biomass‐derived Nitrogen and Phosphorus Co‐doped Hierarchical Micro/mesoporous Carbon Materials for High‐performance Non‐enzymatic H2O2 Sensing

Nitrogen and phosphorus co‐doped hierarchical micro/mesoporous carbon (N,P‐MMC) was prepared by simple thermal treatment of freeze‐dried okra in the absence of any other additives. The 0.96 wt % of N and 1.47 wt % of P were simultaneously introduced into the graphitic framework of N,P‐MMC, which also possesses hierarchical porous structure with mesopores centered at 3.6 nm and micropores centered at 0.79 nm. Most importantly, N,P‐MMC carbon exhibits excellent catalytic activity for electrocatalytic reduction of H₂O₂, resulting in a new strategy to construct non‐enzymatic H₂O₂ sensor. The N,P‐MMC‐based H₂O₂ sensor displays two linear detection range about 0.1 mM–10 mM (R²=0.9993) and 20 mM–200 mM (R²=0.9989), respectively. The detection limit is estimated to be 6.8 μM at a signal‐to‐noise ratio of 3. These findings provide insights into synthesizing functional heteroatoms doped porous carbon materials for biosensing applications.     

A Novel Biomimetic Hydrogen Peroxide Biosensor Based on Pt Flowers‐decorated Fe3O4/Graphene Nanocomposite

A sensitive and selective amperometric H₂O₂ biosensor was obtained by utilizing the electrodeposition of Pt flowers on iron oxide‐reduced graphene oxide (Fe₃O₄/rGO) nanocomposite modified glassy carbon electrode (GCE). The morphology of Fe₃O₄/rGO and Pt/Fe₃O₄/rGO was characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM), respectively. The step‐wise modification and the electrochemical characteristics of the resulting biosensor were characterized by cyclic voltammetry (CV) and chronoamperometry methods. Thanks to the fast electron transfer at the Pt/Fe₃O₄/rGO electrode interface, the developed biosensor exhibits a fast and linear amperometric response upon H₂O₂. The linear range of Pt/Fe₃O₄/rGO is 0.1∼2.4 mM (R²=0.998), with a sensitivity of 6.875 μA/mM and a detection limit of 1.58 μM (S/N=3). In addition, the prepared biosensor also provides good anti‐interferent ability and long‐term stability due to the favorable biocompatibility of the electrode interface. The proposed sensor will become a reliable and effective tool for monitoring and sensing the H₂O₂ in complicate environment.     

Highly Selective Nanostructured Electrochemical Sensor Utilizing Densely Packed Ultrathin Gold Nanowires Film

The number of studies conducted about nonenzymatic electrochemical sensors has increased in recent years due to the development of more stable and robust electrodes using noble metals. One of the key aspects for achieving high sensing performance including detection limit and sensitivity is the design of electrode architecture. Herein, we report a new electrochemical sensing platform featuring ultrathin standing gold nanowires (AuNWs) for nonenzymatic detection of hydrogen peroxide (H₂O₂). The use of AuNWs resulted in an increased electron transfer efficiency due to the higher active surface area compared to traditional gold film electrodes. This sensor demonstrates good selectivity, reproducibility, a linear range up to 49.5 mM of H₂O₂ with a sensitivity of 0.185±0.003 mAmM^?1cm^?2 and a limit of detection of 111 μM. The biological relevance of this sensor was tested in cell culture media to illustrate the performance of the proposed sensing electrode in complex biological media.     

Magnetic loading of carbon nanotube/nano-Fe3O4 composite for electrochemical sensing

An electrochemical sensing platform was developed based on the magnetic loading of carbon nanotube (CNT)/nano-Fe₃O₄ composite on electrodes. To demonstrate the concept, nano-Fe₃O₄ was deposited by the chemical coprecipitation of Fe²⁺ and Fe³⁺ in the presence of CNTs in an alkaline solution. The resulting magnetic nanocomposite brings new capabilities for electrochemical devices by combining the advantages of CNT and nano-Fe₃O₄ and provides an alternative way for loading CNT on electrodes. The fabrication and the performances of the magnetic nanocomposite modified electrodes have been described. Cyclic voltammetry (CV) and constant potential measurement indicated that the incorporated CNT exhibited higher electrocatalytic activity toward the redox processes of hydrogen peroxide. In addition, chitosan (CTS) has also been introduced into the bulk of the CNT/nano-Fe₃O₄ composite by coprecipitation to immobilize glucose oxidase (GOx) for sensing glucose. The marked electrocatalytic activity toward hydrogen peroxide permits effective low-potential amperometric biosensing of glucose, in connection with the incorporation of GOx into CNT/Fe₃O₄/CTS composite. The accelerated electron transfer is coupled with surface renewability. TEM images and XRDs offer insights into the nature of the magnetic composites. The concept of the magnetic loading of CNT nanocomposites indicates great promise for creating CNT-based biosensing devices and expands the scope of CNT-based electrochemical devices.     

A microfluidic electrochemical device for high sensitivity biosensing: Detection of nanomolar hydrogen peroxide

We report herein a simple device for rapid biosensing consisting of a single microfluidic channel made from poly(dimethylsiloxane) (PDMS) coupled to an injector, and incorporating a biocatalytic sensing electrode, reference and counter electrodes. The sensing electrode was a gold wire coated with 5 nm glutathione-decorated gold nanoparticles (AuNPs). Sensitive detection of H₂O₂ based on direct bioelectrocatalysis by horseradish peroxidase (HRP) was used for evaluation. HRP was covalently linked the glutathione–AuNPs. This electrode presented quasi-reversible cyclic voltammetry peaks at ?0.01 V vs. Ag/AgCl at pH 6.5 for the HRP heme Fe^III/Fe^II couple. Direct electrochemical activity of HRP was used to detect H₂O₂ at high sensitivity with a detection limit of 5 nM in an unmediated system.     

Non-enzymatic hydrogen peroxide sensor based on a gold electrode modified with granular cuprous oxide nanowires

Granular nanowires with a diameter of about 60 nm were fabricated from cuprous oxide (Cu₂O) by an electrochemical method using anodic aluminium oxide as the template. A non-enzymatic sensor for hydrogen peroxide (H₂O₂) was then developed on the basis of a gold electrode modified with Cu₂O nanowires and Nafion. The resulting sensor enables the determination of H₂O₂ with a sensitivity of 745 μA?mM^?1?cm^?2, over a wide linear range (0.25 μM to 5.0 mM), and with a low detection limit (0.12 μM). The results demonstrate that the use of such granular nanowires provides a promising tool for the design of non-enzymatic chemical sensors.

Magnetite Nanorods Stabilized by Polyaniline/Reduced Graphene Oxide as a Sensing Platform for Selective and Sensitive Non‐enzymatic Hydrogen Peroxide Detection

In this study, magnetite nanorods stabilized on polyaniline/reduced graphene oxide (Fe₃O₄@PANI/rGO) was synthesized via a wet‐reflux strategy. The possible formation of Fe₃O₄@PANI/rGO was morphologically and structurally verified by field emission scanning electron microscopy (FE‐SEM), Fourier transform infrared (FT‐IR) spectroscopy, Raman spectroscopy, X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). Furthermore, the thermal stability of Fe₃O₄@PANI/rGO was measured by a thermogravimetric analyzer (TGA); the composite had good thermal stability owing to the ceramic nature of Fe₃O₄. The Fe₃O₄@PANI/rGO has been applied as a potential sensing platform for electrochemical detection of hydrogen peroxide (H₂O₂). By the combined efforts of extended active surface area, active carbon support, more catalytic active sites and high electrical conductivity, the Fe₃O₄@PANI/rGO exhibited an improved performance toward the non‐enzymatic detection of H₂O₂ in 0.5 M KOH with a fast response time (5 s), high sensitivity (223.7 μA mM^?1 cm^?2), low limit of detection (4.45 μM) and wide linear range (100 μM–1.5 mM). Furthermore, the fabricated sensor exhibited excellent recovery rates (94.2–104.0 %) during real sample analysis.     

Sensitive electrochemical sensor for hydrogen peroxide using Fe3O4 magnetic nanoparticles as a mimic for peroxidase

A sensor for hydrogen peroxide is described that is based on an indium tin oxide electrode modified with Fe₃O₄ magnetic nanoparticles which act as a mimic for the enzyme peroxidase and greatly improve the analytical performance of the sensor. The amperometric current is linearly related to the concentration of H₂O₂ in the range from 0.2 mM to 2 mM, the regression equation is y?=?-0.5–1.82x, the correlation coefficient is 0.998 (n?=?3), and the detection limit is 0.01 mM (S/N?=?3). The sensor exhibits favorable selectivity and excellent stability.

Electrochemical Conversion of Magnetic Nanoparticles Using Disposable Working Electrode in a 3D‐Printed Electrochemical Cell

Exploration of new property/function of nanomaterials is always a strong impetus in the nanoscience field. Here, a new method of electrochemical conversion (ECC) of magnetic nanoparticles (MNPs) is proposed to endow MNPs with signal generation ability for sensing. Briefly, high potential was applied to split H₂O to generate acid, while Fe₃O₄ MNPs reacted with H⁺ and produce ferric/ferrous ions, which further reacted with K₄Fe(CN)₆ to yield Prussian blue (PB) through potential cycling. The ECC method worked well on both home‐made and commercial MNPs with different sizes. The generated PB possessed strong electrochemical activity for further applications. Interestingly, an uneven deposition of PB on working electrode and undesired contamination of the reference and counter electrodes were found when using commercial integrated three‐electrode chip. A 3D‐printed electrochemical cell was designed to facilitate the ECC and avoid drawbacks of commercial integrated electrode. The 3D‐printed electrochemical cell was proven to solve the problem above through spatial separation of electrodes and thus facilitated the ECC process. An electrochemical sensor for H₂O₂ detection based on the catalysis ability of ECC‐based PB exhibited a linear response from 5 μM to 1 mM, a high sensitivity of 269 μA mM^?1 cm^?2 and a low detection limit of 0.16 μM (S/N=3), which suggests its promising application prospect in electrochemistry‐related analysis.     

Synthesis of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>—Ag nanocomposites and their application to enzymeless hydrogen peroxide detection

To achieve highly sensitive nonenzymatic detection of H₂O₂, a novel electrochemical sensor based on Fe₃O₄-Ag nanocomposites was developed. Nanocomposites were synthesized by reducing [Ag(NH₃)₂]⁺ at the gas/liquid interface in the presence of silver seeds and confirmed by transmission electron microscopy and X-ray diffractometry. Electrochemical investigations indicate that the sensor is able to detect H₂O₂ within a wide linear range of 0.5 μM to 4.0 mM, sensitivity of 135.4 μA mM^?1 cm^?2 and low detection limit of 0.2 μM (S/N = 3). Additionally, the sensor exhibits good anti-interference ability, stability and repeatability. These results show that the Fe₃O₄-Ag nanocomposite is a promising electrocatalytic material for sensors construction.     

Highly Sensitive Electrochemical Hydrogen Peroxide Sensor Based on Iron Oxide‐Reduced Graphene Oxide‐Chitosan Modified with DNA‐Celestine Blue

The present study describes a novel and very sensitive electrochemical assay for determination of hydrogen peroxide (H₂O₂) based on synergistic effects of reduced graphene oxide‐ magnetic iron oxide nanocomposite (rGO‐Fe₃O₄) and celestine blue (CB) for electrochemical reduction of H₂O₂. rGO‐Fe₃O₄ nanocomposite was synthesized and characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X‐ray diffraction (XRD), electrochemical impedance spectroscopy and cyclic voltammetry. Chitosan (Chit) was used for immobilization of amino‐terminated single‐stranded DNA (ss‐DNA) molecules via a glutaraldehyde (GA) to the surface of rGO‐Fe₃O₄. The MTT (3‐(4,5‐Dim ethylt hiazol‐2‐yl)‐2,5‐diphenylt etrazolium bromide) results confirmed the biocompatibility of nanocomposite. Experimental parameters affecting the ss‐DNA molecules immobilization were optimized. Finally, by accumulation of the CB on the surface of the rGO‐Fe₃O₄‐Chit/ssDNA, very sensitive amperometric H₂O₂ sensor was fabricated. The electrocatalytic activity of the rGO‐Fe₃O₄‐Chit/DNA‐CB electrode toward H₂O₂ reduction was found to be very efficient, yielding very low detection limit (DL) of 42 nM and a sensitivity of 8.51 μA/μM. Result shows that complex matrices of the human serum samples did not interfere with the fabricated sensor. The developed sensor provided significant advantages in terms of low detection limit, high stability and good reproducibility for detection of H₂O₂ in comparison with recently reported electrochemical H₂O₂ sensors.     

Noncovalent Assembly of Picket‐Fence Porphyrin on Carbon Nanotubes as Effective Peroxidase‐Like Catalysts for Detection of Hydrogen Peroxide in Beverages

A newly developed electrochemical sensor for determination of hydrogen peroxide (H₂O₂) in beverages using a water‐insoluble picket‐fence porphyrin (FeTpivPP) functionalized multiwalled carbon nanotubes (MWNTs) is demonstrated. Introduction of FeTpivPP on MWNTs led to enhanced electron transfer. As a new platform in electrochemical analysis, the resultant sensor showed excellent electrocatalytic activity toward the reduction of H₂O₂ due to the synergic effect between MWNTs and FeTpivPP, thus leading to highly sensitive amperometric sensing of H₂O₂ with a detection limit of 0.05 µmol L^?1. The developed method is successfully used to detect H₂O₂ in beverages and shows great promise for routine sensing applications.     

Three-dimensional porous reduced graphene oxide decorated with MoS2 quantum dots for electrochemical determination of hydrogen peroxide

Three-dimensional (3D) graphene-based nanomaterials have shown wide applications in electrochemical fields such as biosensors. In this study, we displayed a simple fabrication of 3D structural reduced graphene oxide (3D structural RGO) decorated with molybdenum disulfide quantum dots (MoS₂QDs) through a three-step reaction process. With its abundant raw materials, this strategy is economic and non-toxic. Various characterization techniques were utilized to characterize the morphologies of the synthesized MoS₂QDs, graphene oxide (GO), and 3D structural RGO-MoS₂QDs composites. Simultaneously, X-ray photoelectron spectroscopy was applied to characterize the structure and properties of composites. In order to understand the effects of the reaction period on the structure of 3D structural RGO-MoS₂QDs, a series of samples with various reaction periods were prepared for morphological characterization. Finally, the fabricated 3D structural RGO-MoS₂QDs composites were used to modify a glassy carbon electrode as an electrochemical non-enzymatic hydrogen peroxide (H₂O₂) sensor. The obtained results indicate that the fabricated electrochemical H₂O₂ sensor exhibits a wide detection range (0.01–5.57 mM), low detection limit (1.90 μM), good anti-interference performance, and long-time stability (18 days).     

Porous cuprous oxide microcubes for non-enzymatic amperometric hydrogen peroxide and glucose sensing

Using porous cuprous oxide (Cu₂O) microcubes, a simple non-enzymatic amperometric sensor for the detection of H₂O₂ and glucose has been fabricated. Cyclic voltammetry (CV) revealed that porous Cu₂O microcubes exhibited a direct electrocatalytic activity for the reduction of H₂O₂ in phosphate buffer solution and the oxidation of glucose in an alkaline medium. The non-enzymatic amperometric sensor used in the detection of H₂O₂ with detection limit of 1.5 × 10^?6 M over wide linear detection ranges up to 1.5 mM and with a high sensitivity of 50.6 μA/mM. This non-enzymatic voltammetric sensor was further utilized in detection of glucose with a detection limit of 8.0 × 10^?7 M, a linear detection range up to 500 μM and with a sensitivity of ?70.8 μA/mM.     

Fe2O3-decorated boron/nitrogen-co-doped carbon nanosheets as an electrochemical sensing platform for ultrasensitive determination of paraquat in natural water

Boron/nitrogen-co-doped carbon (BCN) nanosheets decorated with Fe₂O₃ nanocrystals (Fe₂O₃–BCN) were cast on a glassy carbon electrode (GCE) and applied as an electrochemical sensor to effectively detect paraquat (PQ), a toxic herbicide, in aqueous environments. A linear experiment performed using square wave voltammetry (SWV) under optimized experimental conditions produced a decent linear relationship and a low detection limit (LOD) of 2.74 nmol/L (S/N = 3). Repeatability, reproducibility, stability, and interference experiments confirmed that the Fe₂O₃–BCN/GCE system exhibited decent electrochemical sensing performance for PQ molecules. Notably, the designed sensor showed high selectivity and a decent linear relationship with PQ concentration in natural water samples. To the best of our knowledge, this is the first study on the preparation of Fe₂O₃–BCN nanosheets for PQ detection. The proposed sensor can be employed as an effective alternative tool for distinguishing and processing PQ.     

Hybridized Polyoxometalate‐Based Metal–Organic Framework with Ketjenblack for the Nonenzymatic Detection of H2O2

The rational design and development of efficient and affordable enzyme‐free electrocatalysts for electrochemical detection are of great significance for the large‐scale applications of sensor materials, and have aroused increasing research interest. Herein, we report that a typical polyoxometalate (POM)‐based metal–organic framework (NENU5) that was hybridized with ketjenblack (KB) was a highly efficient electrochemical catalyst that could be used for the highly sensitive nonenzymatic detection of H₂O₂. The composite catalyst exhibited superb electrochemical detection performance towards H₂O₂, including a broad linear range from 10–50 mm , a low detection limit of 1.03 μm , and a high sensitivity of 33.77 μA mm ⁻¹, as well as excellent selectivity and stability. These excellent electrocatalytic properties should be attributed to the unique redox activity of the POM, the high specific surface area of the metal–organic framework (MOF), the strong conductivity of KB, and the synergistic effects of the multiple components in the composites during the electrolysis of H₂O₂. This work provides a new pathway for the exploration of nonenzymatic electrochemical sensors.     

Amperometric hydrogen peroxide sensor based on the use of CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> hollow nanostructures

The authors report on the preparation of a hollow-structured cobalt ferrite (CoFe₂O₄) nanocomposite for use in a non-enzymatic sensor for hydrogen peroxide (H₂O₂). Silica (SiO₂) nanoparticles were exploited as template for the deposition of Fe₃O₄/CoFe₂O₄ nanosheets, which was followed by the removal of SiO₂ template under mild conditions. This leads to the formation of hollow-structured Fe₃O₄/CoFe₂O₄ interconnected nanosheets with cubic spinel structure of high crystallinity. The material was placed on a glassy carbon electrode where it acts as a viable sensor for non-enzymatic determination of H₂O₂. Operated at a potential of ?0.45 V vs. Ag/AgCl in 0.1 M NaOH solution, the modified GCE has a sensitivity of 17 nA μM^?1 cm^?2, a linear response in the range of 10 to 1200 μM H₂O₂ concentration range, and a 2.5 μM detection limit. The sensor is reproducible and stable and was applied to the analysis of spiked urine samples, where it provided excellent recoveries.

Open image in new window

Graphical abstract Schematic of a cobalt ferrite (CoFe₂O₄) hollow structure for use in electrochemical determination of H₂O₂. The sensor shows a low detection limit, a wide linear range, and excellent selectivity for H₂O₂.

     

High loading MnO2 nanowires on graphene paper: Facile electrochemical synthesis and use as flexible electrode for tracking hydrogen peroxide secretion in live cells

Recent progress in flexible and lightweight electrochemical sensor systems requires the development of paper-like electrode materials. Here, we report a facile and green synthesis of a new type of MnO₂ nanowires–graphene nanohybrid paper by one-step electrochemical method. This strategy demonstrates a collection of unique features including the effective electrochemical reduction of graphene oxide (GO) paper and the high loading of MnO₂ nanowires on electrochemical reduced GO (ERGO) paper. When used as flexible electrode for nonenzymatic detection of hydrogen peroxide (H₂O₂), MnO₂–ERGO paper exhibits high electrocatalytic activity toward the redox of H₂O₂ as well as excellent stability, selectivity and reproducibility. The amperometric responses are linearly proportional to H₂O₂ concentration in the range 0.1–45.4 mM, with a detection limit of 10 μM (S/N = 3) and detection sensitivity of 59.0 μA cm⁻² mM⁻¹. These outstanding sensing performances enable the practical application of MnO₂–ERGO paper electrode for the real-time tracking H₂O₂ secretion by live cells macrophages. Therefore, the proposed graphene-based nanohybrid paper electrode with intrinsic flexibility, tailorable shapes and adjustable properties can contribute to the full realization of high-performance flexible electrode material used in point-of-care testing devices and portable instruments for in-vivo clinical diagnostics and on-site environmental monitoring.