Gold Nanobone/Carbon Nanotube Hybrids for the Efficient Nonenzymatic Detection of H2O2 and Glucose

We report a facile strategy for the synthesis of gold nanobone/carbon nanotube (CNT@GNB) nanoassemblies, which were prepared through hybridization of CNTs and GNBs mediated by a thiolated pyrene derivative. The SEM images confirmed the successful construction of the CNT@GNB nanoassemblies. Screen printed electrodes modified with the CNT@GNB nanoassemblies exhibited decent electrocatalytic activity, large surface‐to‐volume ratios, high electrochemical reversibility, and efficient electron transport properties, thereby enabling stable and sensitive nonenzymatic detection of H₂O₂ and glucose, with detection limits of 0.8 µM and 0.07 mM, respectively. Moreover, no interference was observed at a potential of +0.38 V for the interfering species, such as ascorbic acid and urea, indicating high selectivity toward the glucose detection.     

Porous Molybdenum Carbide Nanostructured Catalyst toward Highly Sensitive Biomimetic Sensing of H2O2

There are great challenges to fabricate a highly selective and sensitive enzyme‐free biomimetic sensor. Herein for the first time a unique nanostructure of porous molybdenum carbide impregnated in N‐doped carbon (p‐Mo₂C/NC) is synthesized by using SiO₂ nanocrystals‐templating method and is further used as an enzyme‐free electrochemical biosensor toward highly selective, sensitive detection of H₂O₂, of which the limit of detection, dynamic detection range and sensitivity accomplish as 0.22 μM, 0.05–4.5 mM and 577.14 μA mM^?1 cm^?2, respectively, and are much superior to the non‐porous molybdenum carbide impregnated in N‐doped carbon (Mo₂C/NC). The sensor is also used to monitor H₂O₂ released from A549 living cells. This work holds a great promise to be used to monitor the presence of H₂O₂ in biological research while offering an important knowledge to design a highly selective and sensitive biomimetic sensor by synthesizing a porous catalyst to greatly improve the reaction surface area rather than conventionally only relying on dispersing the catalyst material into porous carbon substrate.     

A Novel Enzymatic Glucose Biosensor and Nonenzymatic Hydrogen Peroxide Sensor Based on (3‐Aminopropyl) Triethoxysilane Functionalized Reduced Graphene Oxide

In the present study, a novel enzymatic glucose biosensor using glucose oxidase (GOx) immobilized into (3‐aminopropyl) triethoxysilane (APTES) functionalized reduced graphene oxide (rGO‐APTES) and hydrogen peroxide sensor based on rGO‐APTES modified glassy carbon (GC) electrode were fabricated. Nafion (Nf) was used as a protective membrane. For the characterization of the composites, Fourier transform infrared spectroscopy (FTIR), X‐ray powder diffractometer (XRD), and transmission electron microscopy (TEM) were used. The electrochemical properties of the modified electrodes were investigated using electrochemical impedance spectroscopy, cyclic voltammetry, and amperometry. The resulting Nf/rGO‐APTES/GOx/GC and Nf/rGO‐APTES/GC composites showed good electrocatalytical activity toward glucose and H₂O₂, respectively. The Nf/rGO‐APTES/GC electrode exhibited a linear range of H₂O₂ concentration from 0.05 to 15.25 mM with a detection limit (LOD) of 0.017 mM and sensitivity of 124.87 μA mM⁻¹ cm⁻². The Nf/rGO‐APTES/GOx/GC electrode showed a linear range of glucose from 0.02 to 4.340 mM with a LOD of 9 μM and sensitivity of 75.26 μA mM⁻¹ cm⁻². Also, the sensor and biosensor had notable selectivity, repeatability, reproducibility, and storage stability.     

Glutathione-capped CdTe quantum dots for the sensitive detection of glucose

A simple and sensitive assay system for glucose based on the glutathione (GSH)-capped CdTe quantum dots (QDs) was developed. GSH-capped CdTe QDs exhibit higher sensitivity to H₂O₂ produced from the glucose oxidase catalyzed oxidation of glucose, and are also more biocompatible than other thiols-capped QDs. Based on the quenching of H₂O₂ on GSH-capped QDs, glucose can be detected. The detection conditions containing reaction time, the concentration of glucose oxidase and the sizes of QDs were optimized and the detection limits for glucose was determined to be 0.1 μM; two detection ranges of glucose from 1.0 μM to 0.5 mM and from 1.0 mM to 20 mM, respectively were obtained. The detection limit was almost a 1000 times lower than other QDs-based optical glucose sensing systems. The developed glucose detection system was simple and facile with no need of complicated enzyme immobilization and modification of QDs.     

Preparation of Trace Fe2P Modified N,P Co-doped Carbon Materials and their Application to Hydrogen Peroxide Detection

The determination of hydrogen peroxide (H₂O₂) based on electrochemical sensors is highly attractive in the fields of environmental monitoring and biosensing, however development of non-precious metal-based electrocatalysts with high performances remains challenging. Here, a new non-enzymatic H₂O₂ sensor has been reported by using Fe₂P modified N,P co-doped carbon (Fe₂P/NP-C) materials as sensing materials. Fe₂P/NP-C materials were synthesized by pyrolysis of polydopamine coating Fe-based coordination polymer nanoparticles, which were obtained by direct mixing FeCl₃ and sodium hexametaphosphate at room temperature. The electrochemical tests display that Fe₂P/NP-C-based non-enzymatic H₂O₂ sensor exhibited detection limit of 60 μM and linear range from 0.1 mM to 1 mM, respectively. This work presents a new avenue to design of non-precious metal-based electrocatalysts for chemical sensing and biosensing applications.     

Simple Electrodeposition of Dendritic Pd Without Supporting Electrolyte and Its Electrocatalytic Activity Toward Oxygen Reduction and H2O2 Sensing

Metallic palladium (Pd) electrocatalysts for oxygen reduction and hydrogen peroxide (H₂O₂) oxidation/reduction are prepared via electroplating on a gold metal substrate from dilute (5 to 50 mM) aqueous K₂PdCl₄ solution. The best Pd catalyst layer possessing dendritic nanostructures is formed on the Au substrate surface from 50 mM Pd precursor solution (denoted as Pd‐50) without any additional salt, acid or Pd templating chemical species. The Pd‐50 consisted of nanostructured dendrites of polycrystalline Pd metal and micropores within the dendrites which provide high catalyst surface area and further facilitate reactant mass transport to the catalyst surface. The electrocatalytic activity of Pd‐50 proved to be better than that of a commercial Pt (Pt/C) in terms of lower overpotential for the onset and half‐wave potentials and a greater number of electrons (n) transferred. Furthermore, amperometric i–t curves of Pd‐50 for H₂O₂ electrochemical reaction show high sensitivities (822.2 and ?851.9 µA mM^?1 cm^?2) and low detection limits (1.1 and 7.91 µM) based on H₂O₂ oxidation H₂O₂ reduction, respectively, along with a fast response (<1 s).     

Development of Silver Nanowires Based Highly Sensitive Amperometric Glucose Biosensor

The fabrication of a highly sensitive amperometric glucose biosensor based on silver nanowires (AgNWs) is presented. The electrochemical behavior of glassy carbon electrode modified by Ag NWs exhibits remarkable catalytic performance towards hydrogen peroxide (H₂O₂) and glucose detection. The biosensor could detect glucose in the linear range from 0.005 mM to 10 mM, with a detection limit of 50 µM (S/N=3). The glucose biosensor shows high and reproducible sensitivity of 175.49 µA cm^?2 mM and good stability. In addition, the biosensor exhibits a good anti‐interference ability and favorable stability over relatively long‐term storage (more than 21 days).     

Hydrogen Peroxide Detection at Electrochemically and Sol‐Gel Derived Ir Oxide Films

Ir oxide (IrOx) films, formed electrochemically on bulk Ir metal (Ir/IrOx) and also on sol‐gel (SG) derived non‐silica based nanoparticulate Ir, have been studied as material useful for the detection of hydrogen peroxide, with possible application as a glucose biosensor. H₂O₂ reduction and oxidation on Ir/IrOx and SG‐derived IrOx films, deposited on various substrates such as Pt, Ir and GC, have been compared to the H₂O₂ behavior at the bare substrate. It was found that H₂O₂ reduction proceeds on the underlying electrode substrate, while H₂O₂ oxidation is independent of the nature of the substrate, therefore occurring via the IrOx film. The reactivity of IrOx towards H₂O₂ oxidation is similar to that seen at Pt, although IrOx has the additional advantages of excellent stability, insensitivity to common interfering substances, biocompatibility and a linear range of detection, up to at least 12 mM H₂O_2. At micromolar concentrations of H₂O₂, a second mode of detection, involving the catalyzed growth of IrOx films at Ir substrates, can be employed. These two methods of H₂O₂ analysis (oxidation/reduction and enhanced IrOx growth) can also be employed for glucose detection using IrOx‐based glucose biosensors.     

A Comparison of a Nanostructured Enzymeless Au/Fe2O3/MWCNTs/GCE Electrode and a GOx Modified One in Electrocatalytic Detection of Glucose

Acid functionalized multi‐walled carbon nanotubes (f‐MWCNTs) were decorated with Au and Fe₂O₃ nanoparticles (FeONPs) and deposited on glassy carbon electrode (GCE). The resulting hybrid Au/Fe₂O₃/f‐MWCNTs/GCE electrode and the one further modified by glucose oxidase were compared for detection of glucose. FeONPs and Au were deposited on the f‐MWCNTs by sonication‐assisted precipitation and deposition‐precipitation methods, respectively. The morphology and structure of the samples were characterized by transmission electron microscopy, scanning electron microscopy, X‐ray diffraction and Raman spectroscopy. A uniform distribution of FeONPs with an average size of 5 nm increased the surface area of functionalized nanotubes from 39 to 50 m²/g. The electrocatalytic glucose detection on the modified electrodes was evaluated using cyclic voltammetry and chronoamperometry in 0.1 M phosphate buffer solution at pH 7.0. The non‐enzymatic and enzymatic electrodes show sensitivity of 512.4 and 921.4 mA/mM.cm² and detection limit of 1.7 and 0.9 mM, respectively. The enzymatic and enzymeless electrodes retained more than 70 % and 80 % of their cathodic faradic current after 70 days, respectively. The sensing mechanism of the non‐enzymatic biosensor is described through the reaction of glucose with iron (III) ions, while in the case of enzymatic electrode, glucose is oxidized by glucose oxidase.     

Sensitive Electrochemical Detection of Pb(II) and H2O2 via a Dual-functional Sn-doped Defective Bi2S3 Microspheres

In this work, a dual-functional electrochemical sensor has been proposed based on Sn-doped defective Bi₂S₃ (TDDB) microspheres, which exhibited the excellent electrochemical performance on Pb(II) and H₂O₂ detection. The TDDB offered a satisfied detection limit of 8.0 nM towards Pb(II) with a sensitivity of 96.7 μA ⋅ μM⁻¹. As a H₂O₂ sensor, a high sensitivity of 3540 μA mM⁻¹ cm⁻² was obtained in a linear range from 0.45 mM to 10 mM with a detection limit of 10 nM. Moreover, the electrochemical detection of Pb(II) in Taihu Lake and H₂O₂ in human serum was achieved with high reliability and good recovery.     

Enhancement of the sensitivity and selectivity of oxidation of H2O2 on platinum wire at low working potential by platinization and covering of heteropolypyrrole film for amperometric micro-biosensor construction

A microelectrode for glucose determination was constructed by immobilization of glucose oxidase (GOx) on a platinized platinum (Pt) by electrochemical polymerization of a solution containing GOx, pyrrole, and a substituted pyrrole, 4-(3-pyrrolyl)-4-oxobutyric acid. Due to platinization and covering with the polymerized heteropolypyrrole (hPPy) film, the electrode prepared showed high sensitivity to H₂O₂ at a low potential and significantly reduced the response to electroactive compounds, such as ascorbate, urate and 4-acetamidophenol. Working at 200 mV (vs. SCE) the electrode showed a linear response to glucose from 1.6 to 10 mM with a high sensitivity of 1 μA/mM, whereas the response to 1 mM ascorbate, urate, and 4-acetamidophenol was 0.53 μA, 18 nA and 4 nA, respectively, which was about 2.5%, 1.0% and 1.0% of that at a bare electrode. The stability of the electrode was tested at intervals of three or five days, and each test lasted about two hours. After 6 months examination, only 30% of its activity was lost.     

H2O2-sensitive quantum dots for the label-free detection of glucose

A novel label-free detection system based on CdTe/CdS quantum dots (QDs) was designed for the direct measurement of glucose. Herein we demonstrated that the photoluminescence (PL) of CdTe/CdS QDs was sensitive to hydrogen peroxide (H₂O₂). With d-glucose as a substrate, H₂O₂ that intensively quenched the QDs PL can be produced via the catalysis of glucose oxidase (GOx). Experimental results showed that the decrease of the QDs PL was proportional to the concentration of glucose within the range of 1.8 μM to 1 mM with the detection limit of 1.8 μM under the optimized experimental conditions. In addition, the QD-based label-free glucose sensing platform was adapted to 96-well plates for fluorescent assay, enhancing the capabilities and conveniences of this detection platform. An excellent response to the concentrations of glucose was found within the range of 2-30 mM. Glucose in blood and urine samples was effectively detected via this strategy. The comparison with commercialized glucose meter indicated that this proposed glucose assay system is not only simple, sensitive, but also reliable and suitable for practical application. The high sensitivity, versatility, portability, high-throughput and low cost of this glucose sensor implied its potential in point-of-care clinical diagnose of diabetes and other fields.     

Flow Injection Amperometric Analysis of H2O2 at Platinum Nanoparticles Modified Pencil Graphite Electrode

A Pt nanoparticle modified Pencil Graphite Electrode (PGE) was proposed for the electrocatalytic oxidation and non‐enzymatic determination of H₂O₂ in Flow Injection Analysis (FIA) system. Platinum nanoparticles (PtNPs) electrochemically deposited on pretreated PGE (p.PGE) surface by recording cyclic voltammograms of 1.0 mM of H₂PtCl₆ solution in 0.10 M KCl at scan rate of 50 mV s⁻¹ for 30 cycles. Cyclic voltammograms show that the oxidation peak potential of H₂O₂ shifts from about +700 mV at bare PGE to +50 mV at PtNPs/p.PGE vs. Ag/AgCl /KCl (sat.). It can be concluded that PtNPs/p.PGE exhibits a good electrocatalytic activity towards oxidation of H₂O₂. Then, FI amperometric analysis of H₂O₂ was performed under optimized conditions using a new homemade electrochemical flow cell which was constructed for PGE. Linear range was found as 2.5 μM to 750.0 μM H₂O₂ with a detection limit of 0.73 μM (based on S_b/m of 3). As a result, this study shows the first study on the FI amperometric determination of H₂O₂ at PtNPs/p.PGE which exhibits a simple, low cost, commercially available, disposable sensor for H₂O₂ detection. The proposed electrode was successfully applied to determination of H₂O₂ in real sample.     

pH and H2O2 dual-responsive carbon dots for biocatalytic transformation monitoring

Development of sensitive biosensors for biocatalytic transformations monitoring is in high demand but remains a great challenge. It is ascribed to the current strategies that focused on the single metabolite detection, which may bring about the relatively low sensitivity and false diagnosis result. Herein, we report the design and fabrication of novel carbon dots (CDs) with strong orange light emission, pH and H₂O₂ dual-responsive characteristics. The fluorescence quenching of CDs by H⁺ and H₂O₂ enables the highly sensitive detection of H⁺/H₂O₂-generating biocatalytic transformations. This is exemplified by the glucose oxidase-mediated catalytic oxidation reaction on glucose, in which H⁺ and H₂O₂ would be formed. As compared to the case in which glucose is present, significant fluorescence reduction is detected, and the fluorescence intensity is negatively proportional to glucose concentration. Thus, highly sensitive detection of glucose was readily achieved with a detection limit down to 10.18 nmol/L. The prepared CDs not only realize the highly sensitive detection of glucose, but also allows the probing other substances by changing the enzymes, thus providing a versatile platform, and demonstrating good potential to be used for biocatalytic transformations effective monitoring.     

Minimization of Interferences in Flow Injection Amperometric Glucose Biosensor Based on Oxidation of Enzymatically‐produced H2O2

One of the major problems in amperometric biosensors based on detection of H₂O₂ produced by enzymatic reaction between oxidase enzymes and substrate is the interference of redox active compounds such as ascorbic acid (AA), dopamine (DA) and uric acid (UA). To minimize these interferences, sodium bismuthate was used for the first time as an insoluble pre‐oxidant in the flow injection (FI) amperometric glucose biosensor at a Glucose oxidase (GOx) immobilized Pt/Pd bimetallic modified pre‐anodized pencil graphite electrode (p.PGE). In this context, these interfering compounds were injected into a flow injection analysis (FIA) system using an injector which was filled with NaBiO₃. Thus, these interferents were converted into their redox inactive oxidized forms before reaching the electrode in the flow cell. While glucose was not influenced by the pre‐oxidant in the injector, the huge oxidation peak currents of the interferents decreased significantly in the biosensor. FI amperometric current time curves showed that the AA, DA and UA were minimized by 96 %, 86 %, and 98 % respectively, in the presence of an equivalent concentration of interferences in a 1.0 mM glucose solution. The proposed FI amperometric glucose biosensor exhibits a wide linear range (0.01–10 mM, R²=0.9994) with a detection limit of 2.4×10^?3 mM. Glucose levels in the artificial serum and two real samples were successfully determined using the fabricated FI amperometric biosensor.     

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.     

Smartphone-based colorimetric determination of glucose in food samples based on the intrinsic peroxidase-like activity of nitrogen-doped carbon dots obtained from locusts

In this study, nitrogen-doped carbon dots (N-CDs) with excellent peroxidase-like activity were prepared using locust powder as the carbon source by a self-exothermic reaction. The obtained N-CDs could catalyze the oxidation of the chromogenic substrate 3,3′,5,5′-tetramethylbenzidine (TMB) in the presence of H₂O₂ to generate a blue oxidized product (TMB_ox) with a maximum absorption peak at 654 nm. The catalytic reaction conditions were optimized; furthermore, steady-state kinetic analysis indicated that N-CDs exhibited high affinity toward both TMB and H₂O₂, and the Michaelis-Menten constant (k_m) values were 0.115 mM (TMB) and 0.764 mM (H₂O₂). A smartphone-based colorimetric method was developed for quantitative detection. The 1/L values (L stands for lightness in HSL color space) of the TMB_ox solution were recorded via an iPhone application Color Analyzer. Since H₂O₂ is the by-product of glucose (Glu) oxidation in the presence of glucose oxidase (GOx), a simple, sensitive, and selective smartphone-based colorimetric method was developed for the determination of Glu, and the detection limit was 1.09 μM. The smartphone-based method was successfully applied to determine Glu in different food samples with recoveries in the range of 88.5–109.0 %.     

Self‐Assembled Prussian Blue Nanoparticles Based Electrochemical Sensor for High Sensitive Determination of H2O2 in Acidic Media

In this paper, self‐assembled Prussian blue nanoparticles (PBNPs) on carbon ceramic electrode (CCE) were developed as a high sensitive hydrogen peroxide (H₂O₂) electrochemical sensor. The PBNPs film was prepared by a simple dipping method. The morphology of the PBNPs‐modified CCE was characterized by scanning electron microscopy (SEM). The self‐assembled PB film exhibited sufficient mechanical, electrochemical stability and high sensitivity in compare with other PB based H₂O₂ sensors. The sensor showed a good linear response for H₂O₂ over the concentration range 1 μM–0.26 mM with a detection limit of ca. 0.7 μM (S/N=3), and sensitivity of 754.6 mA M^?1 cm^?2. This work demonstrates the feasibility of self‐assembled PBNPs‐modified CCE for practical sensing applications.     

A novel nonenzymatic biosensor for evaluation of oxidative stress based on nanocomposites of graphene blended with CuI

A high-sensitive nonenzymatic hydrogen peroxide (H₂O₂) biosensor based on cuprous iodide and graphene (CuI/Gr) composites has been explored for the detection of H₂O₂ released by living cells and monitoring the oxidative stress of cells under excellular stimulation. The biosensor properties were evaluated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), amperometric i-t curve, and the redox-competition mode of scanning electrochemical microscopy (SECM). Our observations demonstrate that the CuI/Gr nanocomposites modified glassy carbon electrode (GCE) exhibits excellent catalytic activity for H₂O₂ with relatively low detection limit and a wide linear range from 0.5 μM to 3 mM. Moreover, the redox-competition mode of SECM imaging study further illustrates the improved electrochemical catalytic capability for H₂O₂ reduction with CuI/Gr nanocomposites deposited on graphite electrode. Hence, the as-prepared nonenzymatic H₂O₂ biosensor could be used to detect H₂O₂ release from different kinds of living cells under stimulation while eliminating the interference of ascorbic acid.     

MnO<Subscript>2</Subscript> Nanoparticles and Carbon Nanofibers Nanocomposites with High Sensing Performance Toward Glucose

By combining the advantages of manganese dioxide nanoparticles (MnO₂ NPs) and carbon nanofibers (CNFs), a biosensing electrode surface as a high-performance enzyme biosensor is designed in this work. MnO₂ NPs and CNFs nanocomposites (MnO₂–CNFs) were prepared by using a simple hydrothermal method and then were characterized by scanning electron microscopy, powder X-ray diffraction, fourier transform infrared spectroscopy, energy dispersive spectrometry and electrochemisty. The results showed that MnO₂ NPs are uniformly attached to the surface of CNFs. Meanwhile, the MnO₂–CNFs nanocomposites as a supporting matrix can provide an efficient and advantageous platform for electrochemical sensing applications. On the basis of the improved sensitivity of MnO₂–CNFs modified electrode toward H₂O₂ at low overpotential, a MnO₂–CNFs based glucose biosensor was fabricated by monitoring H₂O₂ produced by an enzymatic reaction between glucose oxidase and glucose. The constructed biosensor exhibited a linear calibration graph for glucose in a concentration range of 0.08–4.6 mM and a low detection limit of 0.015 mM. In addition, the biosensor showed other excellent characteristics, such as high sensitivity and selectivity, short response time, and the relative low apparent Michaelis–Menten constant. Analysis of human urine spiked with glucose at different concentration levels yielded recoveries between 101.0 and 104.8%.