A novel sensitive non-enzymatic glucose sensor

Cu nanoclusters were electrochemically deposited on the film of a Nafion-solubilized multi-wall carbon nanotubes (CNTs) modified glassy carbon electrode (CNTs-GCE), which fabricated a Cu-CNTs composite sensor (Cu-CNTs-GCE) to detect glucose with non-enzyme. The linear range is 7.0×10-7 to 3.5×10-3 mol/L with a high sensitivity of 17.76μA/(mmol L), with a low detection limit 2.1×10-7 mol/L, fast response time (within 5 s), good reproducibility and stability.     

Phosphomolybdic acid functionalized graphene loading copper nanoparticles modified electrodes for non-enzymatic electrochemical sensing of glucose

A sensitive non-enzymatic glucose electrochemical biosensor (Cu/PMo₁₂-GR/GCE) was developed based on the combination of copper nanoparticles (CuNPs) and phosphomolybdic acid functionalized graphene (PMo₁₂-GR). PMo₁₂-GR films were modified on the surface of glassy carbon electrode (GCE) through electrostatic self-assembly with the aid of poly diallyl dimethyl ammonium chloride (PDDA). Then CuNPs were successfully decorated onto the PMo₁₂-GR modified GCE through electrodeposition. The morphology of Cu/PMo₁₂-GR/GCE was characterized by scanning electron microscope (SEM). Cyclic voltammetry (CV) and chronoamperometry were used to investigate the electrochemical performances of the biosensor. The results indicated that the modified electrode displayed a synergistic effect of PMo₁₂-GR sheets and CuNPs towards the electro-oxidation of glucose in the alkaline solution. At the optimal detection potential of 0.50 V, the response towards glucose presented a linear response ranging from 0.10 μM to 1.0 mM with a detection limit of 3.0 × 10⁻² μM (S/N = 3). In addition, Cu/PMo₁₂-GR/GCE possessed a high selectivity, good reproducibility, excellent stability and acceptable recovery, which indicating the potential application in clinical field.     

A highly sensitive non-enzymatic glucose sensor based on a simple two-step electrodeposition of cupric oxide (CuO) nanoparticles onto multi-walled carbon nanotube arrays

A novel, stable and highly sensitive non-enzymatic glucose (Glc) sensor was developed using vertically well-aligned multi-walled carbon nanotubes array (MWCNTs) incorporated with cupric oxide (CuO) nanoparticles. The MWCNTs array was prepared by catalytic chemical vapor deposition on a tantalum (Ta) substrate, while a simple and rapid two-step electrodeposition technique was used to prepare the CuO-MWCNTs nanocomposite. First, Cu nanoparticles were deposited onto MWCNTs at constant potential and then they were oxidized into CuO by potential cycling. The electrocatalytic activity of CuO-MWCNTs array was investigated for Glc under alkaline conditions using cyclic voltammetry and chronoamperometry. The sensor exhibited a linear response up to 3 mM of Glc and sensitivity of 2190 μA mM⁻¹ cm⁻², which is two to three orders of magnitude higher than that of most non-enzymatic Glc sensors reported in the literature. The sensor response time is less than 2 s and detection limit is 800 nM (at signal/noise = 3). When tested with human blood serum samples, the sensor exhibited high electrocatalytic activity, stability, fast response and good selectivity against common interfering species, suggesting its potential to be developed as a non-enzymatic Glc sensor.     

Electrochemical non-enzymatic glucose sensors

The electrochemical determination of glucose concentration without using enzyme is one of the dreams that many researchers have been trying to make come true. As new materials have been reported and more knowledge on detailed mechanism of glucose oxidation has been unveiled, the non-enzymatic glucose sensor keeps coming closer to practical applications. Recent reports strongly imply that this progress will be accelerated in ‘nanoera’. This article reviews the history of unraveling the mechanism of direct electrochemical oxidation of glucose and making attempts to develop successful electrochemical glucose sensors. The electrochemical oxidation of glucose molecules involves complex processes of adsorption, electron transfer, and subsequent chemical rearrangement, which are combined with the surface reactions on the metal surfaces. The information about the direct oxidation of glucose on solid-state surfaces as well as new electrode materials will lead us to possible breakthroughs in designing the enzymeless glucose sensing devices that realize innovative and powerful detection. An example of those is to introduce nanoporous platinum as an electrode, on which glucose is oxidized electrochemically with remarkable sensitivity and selectivity. Better model of such glucose sensors is sought by summarizing and revisiting the previous reports on the electrochemistry of glucose itself and new electrode materials.     

The porous CuO electrode fabricated by hydrogen bubble evolution and its application to highly sensitive non-enzymatic glucose detection

The porous Cu film was deposited on a Pt/Ti/Si substrate by electrochemical deposition accompanied by hydrogen evolution at very high current densities. CuO films with similar morphologies were obtained by subsequent annealing of the porous copper films. The morphology, composition and structure of the porous Cu and porous CuO were investigated by FE-SEM, EDS and XRD methods. The complete transformation of Cu to CuO after annealing was indicated. The sensing performances of the porous CuO film were evaluated in alkaline solution with the porous CuO film showing a wide linearity range from 1 μM to 2.5 mM with sensitivity of 2.9 mA cm⁻² mM⁻¹, and detection limit of 0.14 μM. The sensor showed good selectivity to conventional intermediates such as AA and UA and long term stability.     

A ultrasensitive nonenzymatic glucose sensor based on Cu2O polyhedrons modified Cu electrode

A novel nonenzymatic glucose sensor was successfully fabricated based on the Cu2O polyhedrons covered Cu foil.The Cu2O polyhedrons covered Cu foil was constructed via a facile,low-cost and larger scale producible method.The Cu2O polyhedrons covered Cu foil can be directly used as the working electrode of nonenzymatic glucose sensor,which present good stability and flexibility.The results indicated that the Cu2O polyhedrons modified Cu electrode(Cu2O/Cu electrode) showed high electrocatalytic activity for the oxidation of glucose in alkaline solution.There are two linear regions of glucose concentration for the glucose sensor based on Cu2O/Cu electrode,respectively in 10 mmol/L to 0.53 mmol/L(sensitivity:3029.33 mA(mmol/L) à1 cm à2) and in 0.53-7.53 mmol/L(sensitivity:728.67 mA(mmol/L) à1 cm à2).     

Electrospun palladium (IV)-doped copper oxide composite nanofibers for non-enzymatic glucose sensors

Pd (IV)-doped CuO oxide composite nanofibers (PCNFs) have been successfully fabricated via electrospinning and then employed to construct an amperometric non-enzymatic glucose sensor. The PCNFs based glucose sensors display distinctly enhanced electrocatalytic activity towards the oxidation of glucose, showing significantly lower overvoltage (0.32 V) and ultrafast (1 s) and ultrasensitive current (1061.4 μA mM⁻¹ cm⁻²) response with a lower detection limit of 1.9 × 10⁻⁸ M (S/N = 3). Additionally, excellent selectivity, reproducibility and stability have also been obtained. These results indicate that PCNFs are promising candidates for amperometric non-enzymatic glucose detection.     

Reusable and robust high sensitive non-enzymatic glucose sensor based on Ni(OH)2 nanoparticles

Nickel hydroxide nanoparticles were successfully electrodeposited on graphite electrode (Gr/NiONP) and employed as a robust non-enzymatic glucose sensor. The results of cyclic voltammetry (CV) and chronoamperometry demonstrated that the Gr/NiONP electrode displayed high electrocatalytic activity toward glucose. The oxidation current is directly related to the glucose concentration from 1 μM to 15 mM. Besides, the glucose sensor displayed high sensitivity (2400 μA mM⁻¹ cm⁻²) with a detection limit of 0.53 μM (S/N = 3) in basic solution. Moreover, the sensor showed excellent selectivity, reproducibility and stability properties. The relative standard deviation is 1.2% for 10 successive measurements in 16 μM glucose. Interestingly, the signal for glucose was maintained at 95% of its initial value even after 6 months of storage under ambient conditions. Gr/NiONP electrode has also been tested to detect glucose in human serum with satisfactory results.     

基于纳米MnO2-MWCNTs复合材料修饰的葡萄糖传感器

采用水热法制备了纳米MnO2,并用红外光谱,X射线衍射(XRD)和扫描电子显微镜(SEM)对其进行了表征。将碳纳米管和纳米MnO2分散在壳聚糖溶液中,用滴涂法固定到玻碳电极表面,制成修饰电极。利用计时电流法对该葡萄糖传感器的性能进行了研究,纳米MnO2-MWCNTs复合物对葡萄糖的氧化有明显的催化作用。在优化的条件下,葡萄糖在5.0×10-5～3.0×10-2mol/L浓度范围内,计时电流与浓度之间呈线性关系,检出限为1.5×10-5 mol/L(S/N=3)。对1.0×10-3 mol/L葡萄糖溶液平行测定8次的相对标准偏差(RSD)为2.1%。该传感器可成功用于葡萄糖注射液中葡萄糖的测定,回收率在96.4%～98.6%之间。     

Nonenzymatic glucose sensor based on CuO microfibers composed of CuO nanoparticles

Fluorine tin oxide (FTO) electrode modified by copper oxide microfibers (CuO-MFs) composed of numerous interconnected CuO nanoparticles (CuO-NPs) for nonenzymatic glucose sensor was prepared by electrospinning precursor containing high percentage content of copper nitrate with subsequent calcination. The results of scanning electron microscope (SEM) showed the size of CuO particles composing CuO-MFs depended on the percentage content of copper nitrate in precursor solution. With increasing the percentage content of copper nitrate, the interconnected CuO-NPs would gradually replace the large-size CuO particles to accumulate the CuO-MFs, which have the potential to provide larger surface area and more reaction sites for electrocatalytic activity toward glucose. As a glucose sensor, the CuO-MFs modified FTO electrode prepared by 40 wt.% of copper nitrate exhibited a high sensitivity of 2321 μA mM⁻¹ cm⁻² with a low detection limit of 2.2 nM (signal/noise ratio (S/N) = 3). Additionally, the application of the CuO-MFs modified FTO electrode as a glucose sensor for biological samples was demonstrated with satisfactory results.     

An improved sensitivity non-enzymatic glucose sensor based on a CuO nanowire modified Cu electrode

CuO nanowires have been prepared and applied for the fabrication of glucose sensors with highly enhanced sensitivity. Cu(OH)(2) nanowires were initially synthesised by a simple and fast procedure, CuO nanowires were then formed simply by removing the water through heat treatment. The structures and morphologies of Cu(OH)(2) and CuO nanowires were characterised by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy. The direct electrocatalytic oxidation of glucose in alkaline medium at CuO nanowire modified electrodes has been investigated in detail. Compared to a bare Cu electrode, a substantial decrease in the overvoltage of the glucose oxidation was observed at the CuO nanowire electrodes with oxidation starting at ca. 0.10 V vs. Ag/AgCl (saturated KCl). At an applied potential of 0.33 V, CuO nanowire electrodes produce high and reproducible sensitivity to glucose with 0.49 microA/micromol dm(-3). Linear responses were obtained over a concentration range from 0.40 micromol dm(-3) to 2.0 mmol dm(-3) with a detection limit of 49 nmol dm(-3) (S/N = 3). The CuO nanowire modified electrode allows highly sensitive, low working potential, stable, and fast amperometric sensing of glucose, thus is promising for the future development of non-enzymatic glucose sensors.     

A microfluidic glucose sensor incorporating a novel thread‐based electrode system

An electrochemical sensor for the detection of glucose using thread‐based electrodes and fabric is described. This device is relatively simple to fabricate and can be used for multiple readings after washing with ethanol. The fabrication of the chip consisted of two steps. First, three thread‐based electrodes (reference, working, and counter) were fabricated by painting pieces of nylon thread with either layered silver ink and carbon ink or silver/silver chloride ink. The threads were then woven into a fabric chip with a beeswax barrier molded around the edges in order to prevent leaks from the tested solutions. A thread‐based working electrode consisting of one layer of silver underneath two layers of carbon was selected to fabricate the final sensor system. Using the chip, a PBS solution containing glucose oxidase (GOx) (10 mg/mL), potassium ferricyanide (K₃[Fe(CN)₆]) (10 mg/mL) as mediator, and different concentrations of glucose (0‐25 mM), was measured by cyclic voltammetry (CV). It was found that the current output from the oxidation of glucose was proportional to the glucose concentrations. This thread‐based electrode system is a viable sensor platform for detecting glucose in the physiological range.     

Catalytic amplification based on hole-transporting materials as efficient metal-free electrocatalysts for non-enzymatic glucose sensing

Hole-transporting materials with tunable structures and properties are mainly applied in organic light-emitting diodes as transport layer. But their catalytic properties as signal amplifiers in biological assays are seldom reported. In this paper, a starburst molecule, 4,4,4″-tri(N-carbazolyl)-triphenylamine (TCT), containing a triphenylamine as the central core and three carbazoles as the peripheral functional groups was designed and synthesized. Subsequently, the hole-transporting material based on the TCT polymer, poly(TCT) (PTCT), was achieved via a low-cost electrochemical method and exploited as an efficient metal-free electrocatalyst for non-enzymatic glucose detection. Here, this hole-transporting material served three purposes: electrochemical recognition (owing to hydrogen bonding interaction and the biomimetic microenvironment created by the polymer), electrocatalysis (owing to the hole-transporting capability of triphenylamine and the catalytic property of carbazole), and signal amplification (owing to energy migration along the conductive polymer backbone). The electrocatalytic and sensing performances of the sensor based on PTCT were evaluated in detail. Results revealed that the PTCT film could efficiently catalyze the oxidation of glucose at a less-positive potential (+0.20 V) in the absence of any enzymes. The response to glucose was linear in the concentration range of 1.0–6000 μM, and the detection limit was 0.20 μM. With good stability and selectivity, the proposed sensor could be feasibly applied to detect glucose in practical samples. The encouraging sensing performances suggest that the hole-transporting material is one of the promising biomimetic catalysts for electrocatalysis and relevant fields.     

A novel nonenzymatic fluorescent sensor for glucose based on silica nanoparticles doped with europium coordination compound

Amino-functionalized luminescent silica nanoparticles (LSNPs) doped with the europium(III) mixed complex, Eu(TTA)₃phen with 2-thenoyltrifluoroacetone (TTA) and 1,10-phenanthroline(phen) were synthesized successfully using an revised Stöber method. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier-transform infrared (FTIR), and fluorescence spectroscopy were performed for characterizing the synthesized nanoparticles. In the presence of glucose, the fluorescence intensity of the amino-functionalized LSNPs was enhanced due to the enhanced fluorescence resonance energy transfer. Based on fluorescence-enhancing effect, a simple and sensitive method for the determination of glucose was proposed. Under the optimized experimental conditions, the enhanced fluorescence intensity ratio (ΔF/F₀) was linear with the concentration of glucose (c) in the range of 0.0-180 μg ml⁻¹ with a detection limit of 0.8 μg ml⁻¹ (S/N = 3). The R.S.D. values were 0.33% and 0.37% at the levels of 22.5 and 100 μg ml⁻¹, respectively. The proposed method was applied to the determination of glucose in synthetic samples with satisfactory results. The proposed method was also performed to the analysis of blood glucose in human serum samples and the results were in good agreement with clinical data provided by the hospital, which indicates that the method presented here is not only simple, sensitive, but also reliable and suitable for practical applications.     

An electrochemiluminescent sensor for glucose employing a modified carbon nanotube paste electrode

A carbon nanotube paste (CNTP) electrode and a carbon nanotube paste/glucose oxidase (CNTP/GOx) electrode were prepared, and the electrochemiluminescent (ECL) behavior of luminol in the presence of glucose was investigated in detail at each of these electrodes. Compared to the classical carbon paste (CP) electrode, the CNTP electrode incorporating glucose oxidase greatly enhanced the response of the ECL sensor to glucose due to the electrocatalytic activity of the carbon nanotubes, the specificity of the enzymatic reaction, and the sensitivity of the luminol ECL reaction. Under optimal conditions, the electrode was found to respond linearly to glucose in the concentration range 1.0x10(-6) approximately 2.0x10(-3) mol/L, and the detection limit (defined as the concentration that can be detected at a signal-to-noise ratio of 3) was found to be a glucose concentration of 5.0x10(-7) mol/L. The method used to prepare the CNTP/GOx electrode was very convenient, and the electrode surface could be renewed in the case of fouling by simply polishing or cutting it to expose a new and fully active surface. The relative standard deviations (RSD) were found to be 6.8% and 8.9% for the CNTP electrode and the CNTP/GOx electrode (n=6). The electrode retained 95% of its initial response after two weeks.     

ZnO/石墨烯修饰电极的制备及电化学性能研究

采用水热法合成了纳米氧化锌-氧化石墨烯复合材料,并基于该复合材料构制了一种新型双酚A传感器,研究了该传感器的电化学行为。结果表明,在含8.0×10-5mol/L CTAB的p H 7.0磷酸盐缓冲液中,双酚A在0.573V处出现1个不可逆的氧化峰,具有良好的电化学响应;其氧化峰电流与浓度在1.0×10-8~4.0×10-5mol/L范围内呈良好的线性关系,检出限为5.0×10-9mol/L;对模拟环境水样中双酚A进行3次平行测定的回收率在96.3%~101.9%之间,相对误差在1.2%~3.8%范围内。该传感器具有灵敏度高、线性范围宽的特点。     

A novel nonenzymatic hydrogen peroxide sensor based on multi-wall carbon nanotube/silver nanoparticle nanohybrids modified gold electrode

A novel strategy to fabricate hydrogen peroxide (H₂O₂) sensor was developed based on multi-wall carbon nanotube/silver nanoparticle nanohybrids (MWCNT/Ag nanohybrids) modified gold electrode. The process to synthesize MWCNT/Ag nanohybrids was facile and efficient. In the presence of carboxyl groups functionalized multi-wall carbon nanotubes (MWCNTs), silver nanoparticles (Ag NPs) were in situ generated from AgNO₃ aqueous solution and readily attached to the MWCNTs convex surfaces at room temperature, without any additional reducing reagent or irradiation treatment. The formation of MWCNT/Ag nanohybrids product was observed by transmission electron microscope (TEM), and the electrochemical properties of MWCNT/Ag nanohybrids modified gold electrode were characterized by electrochemical measurements. The results showed that this sensor had a favorable catalytic ability for the reduction of H₂O₂. The resulted sensor could detect H₂O₂ in a linear range of 0.05-17 mM with a detection limit of 5 × 10⁻⁷ M at a signal-to-noise ratio of 3. The sensitivity was calculated as 1.42 μA/mM at a potential of −0.2 V. Additionally, it exhibited good reproducibility, long-term stability and negligible interference of ascorbic acid (AA), uric acid (UA), and acetaminophen (AP).     

An electrochemical ascorbic acid sensor based on palladium nanoparticles supported on graphene oxide

In this study, an electrochemical ascorbic acid (AA) sensor was constructed based on a glassy carbon electrode modified with palladium nanoparticles supported on graphene oxide (PdNPs-GO). PdNPs with a mean diameter of 2.6 nm were homogeneously deposited on GO sheets by the redox reaction between PdCl₄²⁻ and GO. Cyclic voltammetry and amperometric methods were used to evaluate the electrocatalytic activity towards the oxidation of AA in neutral media. Compared to a bare GC or a Pd electrode, the anodic peak potential of AA (0.006 V) at PdNPs-GO modified electrode was shifted negatively, and the large anodic peak potential separation (0.172 V) of AA and dopamine (DA), which could contribute to the synergistic effect of GO and PdNPs, was investigated. A further amperometric experiment proved that the proposed sensor was capable of sensitive and selective sensing of AA even in the presence of DA and uric acid. The modified electrode exhibited a rapid response to AA within 5 s and the amperometric signal showed a good linear correlation to AA concentration in a broad range from 20 μM to 2.28 mM with a correlation coefficient of R = 0.9991. Moreover, the proposed sensor was applied to the determination of AA in vitamin C tablet samples. The satisfactory results obtained indicated that the proposed sensor was promising for the development of novel electrochemical sensing for AA determination.     

Glucose biosensor based on immobilization of glucose oxidase in platinum nanoparticles/graphene/chitosan nanocomposite film

The bionanocomposite film consisting of glucose oxidase/Pt/functional graphene sheets/chitosan (GOD/Pt/FGS/chitosan) for glucose sensing is described. With the electrocatalytic synergy of FGS and Pt nanoparticles to hydrogen peroxide, a sensitive biosensor with a detection limit of 0.6 μM glucose was achieved. The biosensor also has good reproducibility, long-term stability and negligible interfering signals from ascorbic acid and uric acid comparing with the response to glucose. The large surface area and good electrical conductivity of graphene suggests that graphene is a potential candidate as a sensor material. The hybrid nanocomposite glucose sensor provides new opportunity for clinical diagnosis and point-of-care applications.