Amperometric glutamate biosensor based on self-assembling glutamate dehydrogenase and dendrimer-encapsulated platinum nanoparticles onto carbon nanotubes

A novel amperometric biosensor based on self-assembling glutamate dehydrogenase (GLDH) and poly(amidoamine) dendrimer-encapsulated platinum nanoparticles (Pt-PAMAM) onto multiwall carbon nanotubes (CNTs) has been developed for the determination of glutamate. The formation of the self-assembled (GLDH/Pt-PAMAM)_n/CNTs construction was investigated by ζ-potential and high resolution transmission electron microscopy (HRTEM). The results indicated the uniform growth of the layer-by-layer nanostructures onto carboxyl-functionalized CNTs. The electrocatalytic property of the (GLDH/Pt-PAMAM)_n/CNTs modified electrode to glutamate in presence of NAD⁺ (β-nicotinamide adenine dinucleotide, 0.1 mM) was investigated at a low overpotential 0.2 V by electrochemical measurements. The results showed it had series of attractive characteristics, such as a large determination range (0.2-250 μM), a short response time (within 3 s), a high sensitivity (433 μA/mM⁻¹ cm²) and good stability (85% remains after 4 weeks).     

Electrochemical DNA biosensors based on platinum nanoparticles combined carbon nanotubes

Platinum nanoparticles were used in combination with multi-walled carbon nanotubes (MWCNTs) for fabricating sensitivity-enhanced electrochemical DNA biosensor. Multi-walled carbon nanotubes and platinum nanoparticles were dispersed in Nafion, which were used to fabricate the modification of the glassy carbon electrode (GCE) surface. Oligonucleotides with amino groups at the 5′ end were covalently linked onto carboxylic groups of MWCNTs on the electrode. The hybridization events were monitored by differential pulse voltammetry (DPV) measurement of the intercalated daunomycin. Due to the ability of carbon nanotubes to promote electron-transfer reactions, the high catalytic activities of platinum nanoparticles for chemical reactions, the sensitivity of presented electrochemical DNA biosensors was remarkably improved. The detection limit of the method for target DNA was 1.0 × 10⁻¹¹ mol l⁻¹.     

Bienzymatic amperometric biosensor for glucose based on polypyrrole/ceramic carbon as electrode material

A novel amperometric biosensor utilizing two enzymes, glucose oxidase (GOD) and horseradish peroxidase (HRP), was developed for the cathodic detection of glucose. The glucose biosensor was constructed by electrochemical formation of a polypyrrole (PPy) membrane in the presence of GOD on the surface of a HRP-modified sol-gel derived-mediated ceramic carbon electrode. Ferrocenecarboxylic acid (FCA) was used as mediator to transfer electron between enzyme and electrode. In the hetero-bilayer configuration of electrode, all enzymes were well immobilized in electrode matrices and showed favorable enzymatic activities. The amperometric detection of glucose was carried out at +0.16 V (versus saturated calomel reference electrode (SCE)) in 0.1 M phosphate buffer solution (pH 6.9) with a linear response range between 8.0×10⁻⁵ and 1.3×10⁻³ M glucose. The biosensor showed a good suppression of interference in the amperometric detection.     

Nanocomposite based on depositing platinum nanostructure onto carbon nanotubes through a one-pot, facile synthesis method for amperometric sensing

Platinum nanoparticles (Pt NPs) were deposited onto multi-walled carbon nanotubes (MWNTs) through direct chemical reduction without any other stabilizing agents. Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry were employed to characterize the morphology of the as-prepared nanocomposite (noted as Pt NPs-MWNTs) and further identify the Pt NPs on the surface of MWNTs. The nanocomposite demonstrated the ability to electrocatalyze the oxidation of hydrogen peroxide and substantially raises the response current. A sensitivity of 591.33 μA mM⁻¹ cm⁻² was obtained at Pt NPs-MWNTs modified electrode. Thus, we immobilized glucose oxidase (GOD) as a model enzyme on the nanocomposite-based electrode with a thin layer of Nafion to fabricate a glucose biosensor, which showed sensitive and fast response to glucose. The influence of the GOD loading was investigated and the biosensor with an enzyme loading concentration of 10 mg/mL shows optimal performance for glucose detection, that is, a detection limit of 3 μM and a response time of 3 s, respectively.     

Hydrogen peroxide biosensor based on electrodeposition of zinc oxide nanoflowers onto carbon nanotubes film electrode

A new amperometric biosensor for hydrogen peroxide was developed based on adsorption of horseradish peroxidase at the glassy carbon electrode modified with zinc oxide nanoflowers produced by electrodeposition onto multi-walled carbon nanotubes （MWNTs） film. The morphology of the MWNTs/nano-ZnO electrode has been investigated by scanning electron microscopy （SEM）, and the electrochemical performance of the electrode has also been studied by amperometric method. The resulting electrode offered an excellent detection for hydrogen peroxide at -0.11 V with a linear response range of 9.9×10^-7 to 2.9×10^-3 mol/L with a correlation coefficient of 0.991, and response time 〈5 s. The biosensor displays rapid response and expanded linear response range, and excellent stability.     

Nonenzymatic glucose voltammetric sensor based on gold nanoparticles/carbon nanotubes/ionic liquid nanocomposite

In this paper, a novel nonenzymatic glucose voltammetric sensor based on a kind of nanocomposite of gold nanoparticles (GNPs) embedded in multi-walled carbon nanotubes (MWCNTs)/ionic liquid (IL) gel was reported. The surface morphology of this nanocomposite was characterized using X-ray photoelectron spectrometer (XPS), scanning electron microscope (SEM) and transmission electron microscope (TEM), respectively. It can be found that most of GNPs lie close to the ektexine of MWCNTs and the others have obviously inserted the inner of MWCNTs through the defects or ends of MWCNTs, due to the attraction between GNPs and MWCNTs as well as the repulsion between GNPs and IL. Voltammetry was used to evaluate the electrocatalytic activities of the nanocomposite biosensor toward nonenzymatic glucose oxidation in alkaline media. The GNPs embedded in MWCNTs/IL gel have strong and sensitive voltammetric responses to glucose, owing to a possible synergistic effect among GNPs, MWCNTs and IL. Under the optimal condition, the linear range for the detection of the glucose is 5.0-120 μM with the correlation coefficient of 0.998, based on the oxidation peak observed during cathodic direction of the potential sweep. The kinetics and mechanism of glucose electro-oxidation were intensively investigated in this system. This kind of nanocomposite biosensor is also highly resistant toward poisoning by chloride ions and capable of sensing glucose oxidation in the presence of 20 μM uric acid and 70 μM ascorbic acid. This work provides a simple and easy approach to the detection of glucose in body fluid with high sensitivity and excellent selectivity.     

Advanced carbon nanomaterials for electrochemiluminescent biosensor applications

Electrochemiluminescent biosensors are nowadays an established technology in the field of immunosensors and diagnostics. Along with the advent of nanotechnology, the marriage between electrochemiluminescence and nanomaterials results in promising enhancing strategies in many biosensor applications. Among nanomaterials, carbon-based ones are the most used, as (i) scaffolds, (ii) luminophores and (iii) electrode materials of the sensor. In this review, we describe the importance of a rational modification and functionalization of carbon nanomaterials to optimize electrochemiluminescence signal, and we also resume the latest and most relevant applications of electrochemiluminescent biosensors based on carbon nanomaterials.     

Amperometric cholesterol biosensor based on immobilized cholesterol esterase and cholesterol oxidase on conducting polypyrrole films

Fabrication of an amperometric cholesterol biosensor by co-immobilization of cholesterol esterase (ChEt) and cholesterol oxidase (ChOx) onto conducting polypyrrole (PPY) films using electrochemical entrapment technique is described. Electrochemical polymerization was carried out using a two-electrode cell configuration at 0.8 V. Characterization of resulting amperometric biosensor for the estimation of cholesterol has been experimentally determined in terms of linear response range, optimum pH, applied potential, temperature, and shelf-life. These PPY/ChEt/ChOx electrodes can be used for cholesterol ester estimation from 1 to 8 mM and have shelf-life of about 4 weeks at 4 °C during which about 15 estimations of cholesterol ester could be made. The sensitivity of PPY/ChEt/ChOx electrode has been found to be 0.15 μA/mM and the apparent K_m value for this electrode is 9.8 mM. Conductivity of the polymer films found to be about 3×10⁻³ S/cm.     

Microwave plasma treated carbon nanotubes and their electrochemical biosensing application

A convenient microwave plasma treatment method with ammonia precursor was proposed to enhance the solubility of carbon nanotubes (CNTs). The SEM, XRD and FTIR spectra clearly demonstrated that the carbon skeleton structure of the resultant ammonia plasma-treated CNTs (ammonia PT-CNTs) was not destroyed and amine groups of different forms were successfully coupled to CNTs in the MWP treatment process. The ammonia PT-CNTs have excellent solubility in water and are insoluble in nonpolar tetrahydrofuran, and the cyclic voltammograms suggest that the enhanced wetting properties clearly favor faster electron transfer kinetics on the ammonia PT-CNT electrodes. By choosing glucose oxidase as a model enzyme, the application of the ammonia PT-CNTs in construction of biosensors was further investigated. Due to the biocompatibility and electron transfer capability of the ammonia PT-CNTs, the resultant GOD biosensor displayed a good sensing performance. The biosensor has a fast response of less than 10 s, and the response current linearly increases with the glucose concentration in the range of 1.2 × 10⁻⁴ to 7.5 × 10⁻³ M with a detection limit of 1.0 × 10⁻⁵ M.     

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.     

Seed-mediated synthesis of copper nanoparticles on carbon nanotubes and their application in nonenzymatic glucose biosensors

In this paper, for the first time, Cu nanoparticles (CuNPs) were prepared by seed-mediated growth method with Au nanoparticles (AuNPs) playing the role of seeds. Carbon nanotubes (CNTs) and AuNPs were first dropped on the surface of glassy carbon (GC) electrode, and then the electrode was immersed into growth solution that contained CuSO₄ and hydrazine. CuNPs were successfully grown on the surface of the CNTs. The modified electrode showed a very high electrochemical activity for electrocatalytic oxidation of glucose in alkaline medium, which was utilized as the basis of the fabrication of a nonenzymatic biosensor for electrochemical detection of glucose. The biosensor can be applied to the quantification of glucose with a linear range covering from 1.0 × 10⁻⁷ to 5 × 10⁻³ M and a low detection limit of 3 × 10⁻⁸ M. Furthermore, the experiment results also showed that the biosensor exhibited good reproducibility and long-term stability, as well as high selectivity with no interference from other oxidable species.     

Biomolecules-carbon nanotubes doped conducting polymer nanocomposites and their sensor application

A simple method for preparing bio-functionalized soluble single-walled carbon nanotubes (SWNTs) is described. Different proteins such as bovine serum albumin (BSA), cytochrome c and horseradish peroxidase (HRP) were used to solubilize low functionality SWNTs in water aided by sonication. The unbound proteins were removed by column chromatography and the SWNT-protein conjugate was used as the sole anionic dopant in electropolymerization of polypyrrole from polymerization solution at pH above the isoelectric point of the protein to provide a negative charge. The morphology of the polypyrrole with SWNT-protein dopant was found to be three-dimensional and fibrous with wide open interlocking pores in contrast to smooth and cauliflower-like for chloride doped polypyrrole. Enhanced sensor performance was demonstrated for hydrogen peroxide detection on polypyrrole/SWCNT-HRP nanocomposites modified electrode. Such nanocomposites can be potentially applied for other biosensor and bio-fuel cell applications.     

Study of enzyme biosensor based on carbon nanotubes modified electrode for detection of pesticides residue

The paper describes a controllable layer-by-layer （LBL） self-assembly modification technique of multi-walled carbon nanotubes （MWNTs） and poly（diallyldimethylammonium chloride） （PDDA） towards glassy carbon electrode （GCE）, Acetylcholinesterase （ACHE） was immobilized directly to the modified GCE by LBL self-assembly method, the activity value of AChE was detected by using i-t technique based on the modified Ellman method. Then the composition of carbaryl were detected by the enzyme electrode with 0.01U activity value and the detection limit of carbaryl is 10^- 12 g L ^-1 so the enzyme biosensor showed good properties for pesticides residue detection.     

纳米金、碳纳米管和纳米线及其在电化学生物传感器研究中的应用

综述了1995～2007年间,纳米金、碳纳米管和纳米线材料及其在电化学生物传感器研究中的新进展,引用文献60篇.     

Modification of polypyrrole nanowires array with platinum nanoparticles and glucose oxidase for fabrication of a novel glucose biosensor

A novel glucose biosensor, based on the modification of well-aligned polypyrrole nanowires array (PPyNWA) with Pt nanoparticles (PtNPs) and subsequent surface adsorption of glucose oxidase (GOx), is described. The distinct differences in the electrochemical properties of PPyNWA–GOx, PPyNWA–PtNPs, and PPyNWA–PtNPs–GOx electrodes were revealed by cyclic voltammetry. In particular, the results obtained for PPyNWA–PtNPs–GOx biosensor showed evidence of direct electron transfer due mainly to modification with PtNPs. Optimum fabrication of the PPyNWA–PtNPs–GOx biosensor for both potentiometric and amperometric detection of glucose were achieved with 0.2 M pyrrole, applied current density of 0.1 mA cm⁻², polymerization time of 600 s, cyclic deposition of PtNPs from −200 mV to 200 mV, scan rate of 50 mV s⁻¹, and 20 cycles. A sensitivity of 40.5 mV/decade and a linear range of 10 μM to 1000 μM (R² = 0.9936) were achieved for potentiometric detection, while for amperometric detection a sensitivity of 34.7 μA cm⁻² mM⁻¹ at an applied potential of 700 mV and a linear range of 0.1–9 mM (R² = 0.9977) were achieved. In terms of achievable detection limit, potentiometric detection achieved 5.6 μM of glucose, while amperometric detection achieved 27.7 μM.     

Preparation and layer-by-layer self-assembly of positively charged multiwall carbon nanotubes

The report described a method of more stably dispersing oxidized carbon nanotubes (CNTs) by forming complex with polycation and the layer-by-layer self-assembly behavior of the complex with polyanion was studied. The properties of the self-assembled multilayer film containing carbon nanotubes were studied. Cyclic voltammetry, UV-vis-NIR spectroscopy, electrochemical impedance spectroscopy and scanning electron microscopy were used for characterization of film assembly. UV-vis-NIR spectroscopy and cyclic voltammetry study indicated the uniform growth of the film. Electrochemical impedance spectroscopy results showed that incorporating of carbon nanotubes in the polyelectrolyte multilayers decreased in the electron-transfer resistance R_ct, indicating more favorable electrochemical reaction interface. The electrocatalytic property of the multilayer modified electrode to NADH was investigated mainly with different numbers of the bilayers and the results showed that along with the increase of the assembled bilayers the overpotential of NADH oxidation decreased. The detection limit could reach 6 μM at a detection potential of 0.4 V.     

Biocomposites of covalently linked glucose oxidase on carbon nanotubes for glucose biosensor

The formation of covalently linked composites of multi–walled carbon nanotubes (MWCNT) and glucose oxidase (GOD) with high-function density for use as a biosensing interface is described. The reaction intermediates and the final product were characterized by using FT–IR spectroscopy, and the MWCNT-coated GOD nanocomposites were examined by atomic force microscopy (AFM) and transmission electron microscopy (TEM). Interestingly, it was found that the GOD–MWCNT composites are highly water soluble. Electrochemical characterization of the GOD–MWCNT composites that were modified on a glassy carbon electrode shows that the covalently linked GOD retains its bioactivity and can specifically catalyze the oxidation of glucose. The oxidation current shows a linear dependence on the glucose concentration in the solution in the range of 0.5–40 mM with a detection limit of 30 μM and a detection sensitivity of 11.3 μA/mMcm². The present method may provide a way to synthesize MWCNT related composites with other biomolecules and for the construction of enzymatic reaction-based biofuel cells and biosensors. Supported by grants from the National Natural Science Foundation of China (NSFC, No. 20125515; 90206037; 20375016) and the Natural Science Foundation of Jiangsu Province (Grant No. BK 2004210)     

Electropolymerized multiwalled carbon nanotubes/polypyrrole fiber for solid-phase microextraction and its applications in the determination of pyrethroids

A novel solid-phase microextraction (SPME) fiber coated with multiwalled carbon nanotubes/polypyrrole (MWCNTs/Ppy) was prepared with an electrochemical method and used for the extraction of pyrethroids in natural water samples. The results showed that the MWCNTs/Ppy coated fiber had high organic stability, and remarkable acid and alkali resistance. In addition, the MWCNTs/Ppy coated fiber was more effective and superior to commercial PDMS and PDMS/DVD fibers in extracting pyrethroids in natural water samples. Under optimized conditions, the calibration curves were found to be linear from 0.001 to 10 μg mL⁻¹ for five of the six pyrethroids studied, the exception being fenvalerate (which was from 0.005 to 10 μg mL⁻¹), and detection limits were within the range 0.12-0.43 ng mL⁻¹. The recoveries of the pyrethroids spiked in water samples at 10 ng mL⁻¹ ranged from 83 to 112%.     

Flexible supercapacitors based on carbon nanotubes

This review provides an overview of recent progress towards the development of flexible supercapacitors based on macroscopic carbon nanotubes-based electrodes, including one-dimensional (1D) fibers, 2D films, and 3D foams, with a focus on electrode preparation and configuration design as well as their integration with other multifunctional devices.