A facile strategy for nonenzymatic glucose detection

Glassy carbon electrode modified with boron oxide nanoparticles supported on multiwall carbon nanotubes was obtained via a facile approach. The as-prepared modified electrode exhibits excellent electrocatalytic activity toward the redox of glucose in pH 7.0 phosphate buffer solution. The electrochemical response of the modified electrode to glucose shows a linear range of 1.5-260 μM with a correlation coefficient of 0.9986 and the calculated detection limit is 0.8 μM at a signal-to-noise ratio of 3, which makes it useful for developing the electrochemical determination of glucose concentrations without using glucose oxidase at physiological pH.     

Amperometric sensor based on ferrocene-modified multiwalled carbon nanotube nanocomposites as electron mediator for the determination of glucose

A kind of nanocomposite with good dispersion in water was prepared through covalent adsorption of ferrocenecarboxaldehyde on multiwalled carbon nanotubes (MWNTs) for electrical communication between glucose oxidase (GOD) and electrode. The ferrocene-modified multiwalled carbon nanotube nanocomposites (MWNTs-Fc) could be conveniently cast on electrode surfaces. With the aid of chitosan, GOD was then immobilized on the nanostructure film to form a reagentless amperometric sensor for glucose determination. FTIR spectra and cyclic voltammetry were used to characterize the nanocomposites. The presence of both ferrocene as mediator of electron transfer and MWNTs as conductor enhanced greatly the enzymatic response to the oxidation of glucose. The novel biosensor exhibited a fast response toward glucose with a detection limit of 3.0 × 10⁻⁶ mol/L and the linear range extended up to 3.8 × 10⁻³ mol/L.     

Amperometric glucose biosensor based on adsorption of glucose oxidase at platinum nanoparticle-modified carbon nanotube electrode

A new amperometric biosensor, based on adsorption of glucose oxidase (GOD) at the platinum nanoparticle-modified carbon nanotube (CNT) electrode, is presented in this article. CNTs were grown directly on the graphite substrate. The resulting GOD/Pt/CNT electrode was covered by a thin layer of Nafion to avoid the loss of GOD in determination and to improve the anti-interferent ability. The morphologies and electrochemical performance of the CNT, Pt/CNT, and Nafion/GOD/Pt/CNT electrodes have been investigated by scanning electron microscopy, cyclic voltammetry, and amperometric methods. The excellent electrocatalytic activity and special three-dimensional structure of the enzyme electrode result in good characteristics such as a large determination range (0.1-13.5mM), a short response time (within 5s), a large current density (1.176 mA cm(-2)), and high sensitivity (91mA M(-1)cm(-2)) and stability (73.5% remains after 22 days). In addition, effects of pH value, applied potential, electrode construction, and electroactive interferents on the amperometric response of the sensor were investigated and discussed. The reproducibility and applicability to whole blood analysis of the enzyme electrode were also evaluated.     

Carbon nanotube/cobalt hexacyanoferrate nanoparticle-biopolymer system for the fabrication of biosensors

Cobalt hexacyanoferrate nanoparticles (CoNP) can be easily prepared by mixing hexacyanoferrate and cobalt chloride solution at room temperature. The nanoparticles were solubilized in aqueous solution of a biopolymer chitosan (CHIT). With the introduction of carbon nanotubes (CNT), the CoNP-CNT-CHIT system formed shows synergy between CNT and CoNP with the significant improvement of redox activity of CoNP due to the excellent electron-transfer ability of CNT. The CoNP-CNT-CHIT film modified glassy carbon electrode allows low potential detection of hydrogen peroxide with high sensitivity and fast response time. In particular, with the introduction of CNT, it amplified the H2O2 sensitivity by approximately 70 times compared to film of CoNP-CHIT. With the immobilization of glucose oxidase onto the electrode surface using glutaric dialdehyde, a biosensor that responds sensitively to glucose has been constructed. In pH 6.98 phosphate buffer, interference free determination of glucose has been realized at -0.2V versus saturated calomel electrode (SCE) with a linear range from 0.01 to 10 mM and response time<10s. The detection limit was 5 microM glucose (S/N=3).     

A sensitive nonenzymatic glucose sensor in alkaline media with a copper nanocluster/multiwall carbon nanotube-modified glassy carbon electrode

Copper (Cu) nanoclusters were electrochemically deposited on the film of a Nafion-solubilized multiwall carbon nanotube (CNTs)-modified glassy carbon electrode (CNTs-GCE), which fabricated a Cu-CNTs composite sensor (Cu-CNTs-GCE) to detect glucose with nonenzyme. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) were used for the characterization of the distribution of the Cu nanoclusters on the CNTs matrix. The composite of the Cu-CNTs was investigated by the electrochemical characterization of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The preliminary study shows that the nonenzymatic sensor has synergistic electrocatalytic activity to the oxidation of glucose in alkaline media. A well applicable sensor was constructed to use for the analysis of the glucose in real blood serum samples due to the large number of electrons taking part in the oxidation process, the high apparent kinetic rate constant, and the stable operation of the electrode. The linear range for the detection of the glucose is 7.0 x 10(-7) to 3.5 x 10(-3) M with a high sensitivity of 17.76 microA mM(-1), a low detection limit of 2.1 x 10(-7) M, and a fast response time of within 5s. Experiment results also showed that the sensor has good reproducibility and long-term stability and is interference free.     

Fabrication of bienzyme nanobiocomposite electrode using functionalized carbon nanotubes for biosensing applications

Mediated biosensors consisting of an oxidase and peroxidase (POx) have attracted increasing attention because of their wider applicability. This work presents a novel approach to fabricate nanobiocomposite bienzymatic biosensor based on functionalized multiwalled carbon nanotubes (MWNTs) with the aim of evaluating their ability as sensing elements in amperometric transducers. Electrochemical behavior of the bienzymatic nanobiocomposite biosensor is investigated by Faradaic impedance spectroscopy and cyclic voltammetry. The results indicate that glucose oxidase (GOD) and horseradish peroxidase (HRP) are strongly adsorbed on the surface of the thionin (TH) functionalized MWNTs and demonstrate a facile electron transfer between immobilized GOD/HRP and the electrode via the functionalized MWNTs in a Nafion film. The functionalized carbon nanotubes act as molecular wires to allow efficient electron transfer between the underlying electrode and the redox centres of enzymes through TH. Linear ranges for these electrodes are from 10 nM to 10 mM for glucose and 17 nM to 56 mM for hydrogen peroxide with the detection limit of 3 and 6 nM, respectively. A remarkable feature of the bienzyme electrode is the possibility to determine glucose and hydrogen peroxide at a very low applied potential where the noise level and interferences from other electroactive compounds are minimal. Performance of the biosensor is evaluated with respect to response time, detection limit, selectivity, temperature and pH as well as operating and storage stability.     

Immobilization of glucose oxidase on electrodeposited nickel oxide nanoparticles: direct electron transfer and electrocatalytic activity

For the first time glucose oxidase (GOx) was successfully co-deposited on nickel-oxide (NiO) nanoparticles at a glassy carbon electrode. In this paper we present a simple fabrication method of biosensor which can be easily operated without using any specific reagents. Cyclic voltammetry was used for electrodeposition of NiO nanoparticle and GOx immobilization. The direct electron transfer of immobilized GOx displays a pair of well defined and nearly reversible redox peaks with a formal potential (E(0')) of -0.420 V in pH 7 phosphate buffer solution and the response shows a surface controlled electrode process. The surface coverage and heterogeneous electron transfer rate constant (k(s)) of GOx immobilized on NiO film glassy carbon electrode are 9.45 x 10(-13)mol cm(-2) and 25.2+/-0.5s(-1), indicating the high enzyme loading ability of the NiO nanoparticles and great facilitation of the electron transfer between GOx and NiO nanoparticles. The biosensor shows excellent electrocatalytical response to the oxidation of glucose when ferrocenmethanol was used as an artificial redox mediator. Furthermore, the apparent Michaelis-Menten constant 2.7 mM, of GOx on the nickel oxide nanoparticles exhibits excellent bioelectrocatalytic activity of immobilized enzyme toward glucose oxidation. In addition, this glucose biosensor shows fast amperometric response (3s) with the sensitivity of 446.2nA/mM, detection limit of 24 microM and wide concentration range of 30 microM to 5mM. This biosensor also exhibits good stability, reproducibility and long life time.     

Enzymatically induced formation of neodymium hexacyanoferrate nanoparticles on the glucose oxidase/chitosan modified glass carbon electrode for the detection of glucose

The formation of neodymium hexacyanoferrate (NdHCF) nanoparticles (NPs) on the surface of glucose oxidase/chitosan (GOx/CHIT) modified glass carbon electrode induced by enzymatic reaction was described and characterized. CHIT can be used not only as enzyme immobilizer, but also to provide active sites for NPs growth. Results showed that the optimized conditions of the GOx/CHIT film induced NdHCF NPs for the biosensing of glucose were 1.0mM Nd(3+) and 20.0mM Fe(CN)(6)(3-). The biocatalyzed generation of NdHCF NPs enabled the development of an electrochemical biosensor for glucose. The calculated apparent Michaelis-Menten constant was 7.5mM. The linear range for glucose detection was 0.01-10.0mM with the correlation coefficient of 0.9946, and the detection limit was 5muM (S/N=3). Furthermore, this system avoids the interferences of other species during the biosensing process and can be used for the determination of glucose in human plasma samples.     

Electrodeposited nonconducting polytyramine for the development of glucose biosensors

Biosensors with the composition of carbon/Prussian blue/(glucose oxidase+glutaraldehyde+polytyramine) were constructed. Before tyramine monomers were electropolymerized, glucose oxidase and tyramine monomers were cross-linked with glutaraldehyde onto the surface of Prussian-blue-modified electrodes. The constructed biosensors produced highly reproducible and stable devices. The biosensors exhibited neglectable decrease in current response after 10 repeated uses or after 1 month of dry storage. The resultant biosensors had a linear range of 0.1-1 mM glucose and a detection limit of 0.05 mM. Since the following electrocatalytic process proceeds at a low electrode potential (ca. -0.3 V vs Ag/AgCl), ascorbate and uric acid do not produce observable interfering signal for the determination of glucose.     

The direct electron transfer of glucose oxidase and glucose biosensor based on carbon nanotubes/chitosan matrix

The glucose oxidase (GOD) is entrapped in the composite of carbon nanotubes/chitosan and direct electron transfer reaction between GOD and electrode takes place. The electron transfer rate of GOD is greatly enhanced to 7.73 s(-1) in the system, which is more than one-fold higher than that of flavin adenine dinucleotide adsorbed on the carbon nanotubes (3.1 s(-1)). This maybe results from the conformational change of GOD in the microenvironment enabling the accessibility of active site for GOD to the electrode. Additionally, the bioactivity of GOD modified in the composite on electrode surface is kept. So as-prepared electrode can be used as a glucose biosensor exhibiting higher sensitivity (0.5 microA mM(-1)) and better stability. The facile procedure of immobilizing GOD will promote the developments of electrochemical research for protein, biosensors and other bioelectrochemical devices.     

Glucose biosensor based on electrodeposition of platinum nanoparticles onto carbon nanotubes and immobilizing enzyme with chitosan-SiO(2) sol-gel

A novel amperometric biosensor, based on electrodeposition of platinum nanoparticles onto multi-walled carbon nanotube (MWNTs) and immobilizing enzyme with chitosan-SiO(2) sol-gel, is presented in this article. MWNTs were cast on the glass carbon (GC) substrate directly. An extra Nafion coating was used to eliminate common interferents such as acetaminophen and ascorbic acids. The morphologies and electrochemical performance of the modified electrodes have been investigated by scanning electron microscopy (SEM) and amperometric methods, respectively. The synergistic action of Pt and MWNTs and the biocompatibility of chitosan-SiO(2) sol-gel made the biosensor have excellent electrocatalytic activity and high stability. The resulting biosensor exhibits good response performance to glucose with a wide linear range from 1 microM to 23 mM and a low detection limit 1 microM. The biosensor also shows a short response time (within 5s), and a high sensitivity (58.9 microAm M(-1)cm(-2)). In addition, effects of pH value, applied potential, rotating rate, electrode construction and electroactive interferents on the amperometric response of the sensor were investigated and discussed in detail.     

Enzyme entrapped polypyrrole modified electrode for flow-injection determination of glucose

Immobilization of glucose oxidase in electropolymerized polypyrrole film on the surface of a platinum wire electrode, provides a convenient sensor for flow-injection glucose determination. An upper limit of linear response for 100 microliters injected sample volume was estimated as 20 mM, whereas a 500 microliters injected sample volume gave an estimated detection limit of 0.5 mM. A simple electrode preparation procedure allows quick electrode renewal before each series of measurements.     

Direct electrochemistry of glucose oxidase and biosensing for glucose based on boron-doped carbon nanotubes modified electrode

Due to their unique physicochemical properties, doped carbon nanotubes are now extremely attractive and important nanomaterials in bioanalytical applications. In this work, selecting glucose oxidase (GOD) as a model enzyme, we investigated the direct electrochemistry of GOD based on the B-doped carbon nanotubes/glassy carbon (BCNTs/GC) electrode with cyclic voltammetry. A pair of well-defined, quasi-reversible redox peaks of the immobilized GOD was observed at the BCNTs based enzyme electrode in 0.1M phosphate buffer solution (pH 6.98) by direct electron transfer between the protein and the electrode. As a new platform in glucose analysis, the new glucose biosensor based on the BCNTs/GC electrode has a sensitivity of 111.57 microA mM(-1)cm(-2), a linear range from 0.05 to 0.3mM and a detection limit of 0.01mM (S/N=3). Furthermore, the BCNTs modified electrode exhibits good stability and excellent anti-interferent ability to the commonly co-existed uric acid and ascorbic acid. These indicate that boron-doped carbon nanotubes are the good candidate material for the direct electrochemistry of the redox-active enzyme and the construction of the related enzyme biosensors.     

Electrochemical imprinted sensor for determination of oleanic acid based on poly (sodium 4-styrenesulfonate-co-acrylic acid)-grafted multi-walled carbon nanotubes-chitosan and cobalt hexacyanoferrate nanoparticles

A novel sensitive and selective imprinted electrochemical sensor for the determination of oleanic acid was constructed on a carbon electrode by stepwise modification of functional multi-walled carbon nanotubes, cobalt hexacyanoferrate nanoparticles and a thin imprinted sol-gel film. The fabrication of a homogeneous porous poly (sodium 4-styrenesulfonate-co-acrylic acid)-grafted multi-walled carbon nanotubes/SiO(2)-chitosan nanocomposite film was conducted by controllable electrodeposition technology. The surface morphologies of the modified electrodes were characterized by scanning electron microscope. The performance of the imprinted sensor was investigated by cyclic voltammetry, square wave voltammetry and electrochemical impedance spectroscopy in detail. The imprinted sensor displayed high sensitivity and selectivity towards oleanic acid. A linear relationship between the sensor response signal and the logarithm of oleanic acid concentrations ranging from 1.0×10(-8) to 1.0×10(-3) mol L(-1) was obtained with a detection limit of 2.0×10(-9) mol L(-1). It was applied to the determination of oleanic acid in real capsule samples successfully.     

Detection of glucose using immobilized bienzyme on cyclic bisureas–gold nanoparticle conjugate

A highly sensitive electrochemical glucose sensor has been developed by the co-immobilization of glucose oxidase (GOx) and horseradish peroxidase (HRP) onto a gold electrode modified with biocompatible cyclic bisureas–gold nanoparticle conjugate (CBU–AuNP). A self-assembled monolayer of mercaptopropionic acid (MPA) and CBU–AuNP was formed on the gold electrode through a layer-by-layer assembly. This modified electrode was used for immobilization of the enzymes GOx and HRP. Both the HRP and GOx retained their catalytic activity for an extended time, as indicated by the low value of Michaelis–Menten constant. Analytical performance of the sensor was examined in terms of sensitivity, selectivity, reproducibility, lower detection limit, and stability. The developed sensor surface exhibited a limit of detection of 100 nM with a linear range of 100 nM to 1 mM. A high sensitivity of 217.5 μA mM⁻¹ cm⁻² at a low potential of −0.3 V was obtained in this sensor design. Various kinetic parameters were calculated. The sensor was examined for its practical clinical application by estimating glucose in human blood sample.     

Study of carbon nanotube modified biosensor for monitoring total cholesterol in blood

A carbon nanotube modified biosensor for monitoring total cholesterol in blood was studied. This sensor consists of a carbon working electrode and a reference electrode screen-printed on a polycarbonate substrate. Cholesterol esterase, cholesterol oxidase, peroxidase and potassium ferrocyanide were immobilized on the screen-printed carbon electrodes. Multi-walled carbon nanotubes (MWCN) were added to prompt electron transfer. Experimental results show that the carbon nanotube modified biosensor offers a reliable calibration profile and stable electrochemical properties.     

A novel non-enzymatic ECL sensor for glucose using palladium nanoparticles supported on functional carbon nanotubes

A novel non-enzymatic electrochemiluminescence (ECL) sensor based on palladium nanoparticles (PdNPs)–functional carbon nanotubes (FCNTs) was discovered for glucose detection. PdNPs were homogeneously modified on FCNTs using a facile spontaneous redox reaction method. Their morphologies were characterized by transmission electron microscopy (TEM). Based on ECL experimental results, the PdNPs–FCNTs–Nafion film modified electrode displayed high electrocatalytic activity towards the oxidation of glucose. The free radicals generated by the glucose oxidation reacted with the luminol anion (LH⁻), and enhanced the ECL signal. Under the optimized conditions, the linear response of ECL intensity to glucose concentration was valid in the range from 0.5 to 40 μmol L⁻¹ (r² = 0.9974) with a detection limit (S/N = 3) of 0.09 μmol L⁻¹. In addition, the modified electrode presented high resistance towards the poisoning of chloride ion, high selectivity and long-term stability. In order to verify the sensor reliability, it was applied to the determination of glucose in glucose injection samples. The results indicated that the proposed approach provided a highly sensitive, more facile method with good reproducibility for glucose determination, promising the development of a non-enzymatic ECL glucose sensor.     

Nonenzymatic electrochemical detection of glucose using well-distributed nickel nanoparticles on straight multi-walled carbon nanotubes

A nonenzymatic electrochemical sensor device was fabricated for glucose detection based on nickel nanoparticles (NiNPs)/straight multi-walled carbon nanotubes (SMWNTs) nanohybrids, which were synthesized through in situ precipitation procedure. SMWNTs can be easily dispersed in solution after mild sonication pretreatment, which facilitates the precursor of NiNPs binding to their surface and results in the homogeneous distribution of NiNPs on the surface of SMWNTs. The morphology and component of the nanohybrids were characterized by scanning electron microscopy (SEM) and X-ray powder diffraction (XRD), respectively. Cyclic voltammetry (CV) and amperometry were used to evaluate the catalytic activity of the NiNPs/SMWNTs nanohybrids modified electrode towards glucose. It was found that the nanohybrids modified electrode showed remarkably enhanced electrocatalytic activity towards the oxidation of glucose in alkaline solution compared to that of the bare glass carbon electrode (GCE), the NiNPs and the SMWNTs modified electrode, attributing to the synergistic effect of SMWNTs and Ni²⁺/Ni³⁺ redox couple. Under the optimal detection conditions, the as-prepared sensors exhibited linear behavior in the concentration range from 1 μM to 1 mM for the quantification of glucose with a limit of detection of 500 nM (3σ). Moreover, the NiNPs/SMWNTs modified electrode was also relatively insensitive to commonly interfering species such as ascorbic acid (AA), uric acid (UA), dopamine (DA), galactose (GA), and xylose (XY). The robust selectivities, sensitivities, and stabilities determined experimentally indicated the great potential of NiNPs/SMWNTs nanohybrids for construction of a variety of electrochemical sensors.     

A novel nanobiocomposite based glucose biosensor using neutral red functionalized carbon nanotubes

The performance of a new glucose biosensor based on the combination of biocatalytic activity of glucose oxidase (GOx) with the electrocatalytic properties of CNTs and neutral red (NR) for the determination of glucose is described. This sensor is comprised of a multiwalled carbon nanotubes (MWNTs) conduit functionalized with NR and Nafion (Nf) as a binder and glucose oxidase as a biocatalyst. Neutral red was covalently immobilized on carboxylic acid groups of the CNTs via carbodiimide reaction. The functionalized MWNTs were characterized by microscopic, spectroscopic and thermal methods. The MWNT-NR-GOx-Nf nanobiocomposite was prepared by mixing the GOx solution with NR functionalized CNTs followed by mixing homogeneously with Nafion. The performance of the MWNT-NR-GOx-Nf nanobiocomposite modified electrode was examined by electrochemical impedance spectroscopy and cyclic voltammetry. The catalytic reduction of hydrogen peroxide liberated from the enzymatic reaction of glucose oxidase upon glucose with NR functionalized CNTs leads to the selective detection of glucose. The excellent electrocatalytic activity and the influence of nanobiocomposite film result in good characteristics such as low potential detection of glucose with a large determination range from 1 x 10(-8) to 1 x 10(-3)M with a detection limit of 3 x 10(-9)M glucose, a short response time (with 4s), good stability and anti-interferent ability. The improved electrocatalytic activity and stability made the MWNT-NR-GOx-Nf nanobiocomposite biosensor system a potential platform to immobilize different enzymes for other bioelectrochemical applications.     

Platinum nanoparticles-doped sol-gel/carbon nanotubes composite electrochemical sensors and biosensors

Platinum nanoparticle-doped sol-gel solution is prepared and used as a binder for multi-walled carbon nanotubes (CNT) for the fabrication of electrochemical sensors. Amine group containing sol-gel solution is selected to utilize the affinity of -NH(2) groups toward metal nanoparticles for stabilization the nanoparticles in solution. The resulting CNT-silicate material brings new capabilities for electrochemical devices by using the synergistic action of the electrocatalytic activity of Pt nanoparticles and CNT. The combined electrocatalytic activity permits low-potential detection of hydrogen peroxide with remarkably improved sensitivity. With the incorporation of glucose oxidase within the Pt-CNT-silicate matrix, a Pt-CNT paste-based biosensor has been constructed that responds more sensitively to glucose than CNT-based biosensor. The influences of the composite of the sol-gel solution, the quantity of the solution and the Pt nanoparticles loading are examined. In pH 6.98 phosphate buffer, almost interference free determination of glucose is realized at 0.1 V versus SCE with a linear range from 1 to 25 mM, a response time <15s, and the sensitivity is 0.98 microA mM(-1)cm(-2). The sensitivity of the Pt-CNT paste-based biosensor is almost four times larger than that of the CNT-based biosensor (0.27 microA mM(-1)cm(-2) at 0.1 V). The improved electrocatalytic activity and surface renewability made the Pt-CNT-silicate system a potential platform to immobilize different enzymes for other bioelectrochemical applications.