Synergistic contributions of multiwall carbon nanotubes and gold nanoparticles in a chitosan–ionic liquid matrix towards improved performance for a glucose sensor

We report an ingenious approach for the fabrication of a promising glucose sensor, GOx/Au/CS–IL–MWNT(SH), that exploits the synergistic beneficial characteristics of multiwalled-carbon nanotubes (MWNTs), gold nanoparticles (AuNPs), chitosan (CS) and room temperature ionic liquid (RTIL). Direct electron transfer between glucose oxidase (GOx) and electrode was achieved. Scanning electron microscopy and atomic force microscopy images of GOx/Au/CS–IL–MWNT(SH) reveal that MWNTs and AuNPs are dispersed in CS–IL matrix. Cyclic voltammetry, impedance spectroscopy and chronoamperometry were used to evaluate the performance of biosensor. The GOx/Au/CS–IL–MWNT(SH) biosensor exhibits a linear current response to glucose concentration (1–10 mM) at a low potential of 0.10 V and precludes interferences from uric acid and ascorbic acid. The GOx/Au/CS–IL–MWNT(SH) biosensor has superior performances over GOx/CS–IL–MWNT(SH).     

Glucose biosensor based on new carbon nanotube-gold-titania nano-composites modified glassy carbon electrode

In this paper, a novel biosensor was prepared by immobilizing glucose oxidase （GOx） on carbon nanotube-gold-titania nanocomposites （CNT/Au/TiO2） modified glassy carbon electrode （GCE）. SEM was initially used to investigate the surface morphology of CNT/Au/TiO2 nanocomposites modified GCE, indicating the formation of the nano-porous structure which could readily facilitate the attachment of GOx on the electrode surface. Cyclic voltammogram （CV） and electrochemical impedance spectrum （EIS） were further utilized to explore relevant electrochemical activity on CNT]Au/TiO2 nanocomposites modified GCE. The observations demonstrated that the immobilized GOx could efficiently execute its bioelectrocatalytic activity for the oxidation of glucose. The biosensor exhibited a wider linearity range from 0.1 mmol L-1 to 8 mmol L^-1 glucose with a detection limit of 0.077 mmol L^- 1.     

Multilayer structured carbon nanotubes/poly-l-lysine/laccase composite cathode for glucose/O2 biofuel cell

Multilayer film of laccase, poly-l-lysine (PLL) and multi-walled carbon nanotubes (MWNTs) were prepared by a layer-by-layer self-assembly technique. The results of the UV–vis spectroscopy and scanning electron microscopy studies demonstrated a uniform growth of the multilayer. The catalytic behavior of the modified electrode was investigated. The (MWNTs/PLL/laccase)_n multilayer modified electrode catalyzed four-electron reduction of O₂ to water, without any mediator. The possible application of the laccase-catalyzed O₂ reduction at the (MWNTs/PLL/laccase)_n multilayer modified ITO electrode was illustrated by constructing a glucose/O₂ biofuel cell with the (MWNTs/thionine/AuNPs)₈ GDH film modified ITO electrode as a bioanode and the (MWNTs/PLL/laccase)₁₅ film modified ITO electrode as a biocathode. The open-circuit voltage reached to 700 mV, and the maximum power density achieved 329 μW cm⁻² at 470 mV of the cell voltage.     

Direct-growth of polyaniline nanowires for enzyme-immobilization and glucose detection

Amperometric enzyme biosensor based on the glucose oxidase (GOx) incorporated polyaniline nanowires (PANI-NWs) on carbon cloth (CC) electrode was demonstrated. The simple, direct-growth of PANI-NWs on CC, via electrochemical polymerization, provides free-standing, template-independent, hence almost (interfacial) defects-free nanostructures. The defect-free interfaces, along with the excellently sensitive organic nanostructured-surface, as evident from its significantly large effective surface area (24 times the geometric area) for redox-sensing, allows efficient entrapment/immobilization and sensing of biomolecules, via rapid electron-transfer at NWs-CC. The GOx-immobilized PANI-NWs/CC, even in initial unoptimized stage, exhibited an excellent sensitivity, ～2.5 mA mM^?1 cm^?2, to glucose, over detection range 0–8 mM, adequate for clinical monitoring of human glucose levels. The report clearly reveals a cost-effective simple system possessing enormous potentiality for biosensors, bioenergy and bioelectronics applications.     

Amperometric glucose sensor based on glucose oxidase immobilized on gelatin-multiwalled carbon nanotube modified glassy carbon electrode

We investigated the direct electrochemistry of glucose oxidase (GOx) at gelatin-multiwalled carbon nanotube (GCNT) modified glassy carbon electrode (GCE). GOx was covalently immobilized onto GCNT modified GCE through the well known glutaraldehyde (GAD) chemistry. The immobilized GOx showed a pair of well-defined reversible redox peaks with a formal potential (E⁰′) of ? 0.40 V and a peak to peak separation (ΔE_p) of 47 mV. The surface coverage concentration (Г) of GOx in GCNT/GOx/GAD composite film modified GCE was 3.88 × 10^? 9 mol cm^? 2 which indicates the high enzyme loading. The electron transfer rate constant (k_s) of GOx immobilized onto GCNT was 1.08 s^? 1 which validates a rapid electron transfer processes. The composite film shows linear response towards 6.30 to 20.09 mM glucose. We observed a good sensitivity of 2.47 μA mM^?1 cm^? 2 for glucose at the composite film. The fabricated biosensor displayed two weeks stability. Moreover, it shows no response to 0.5 mM of ascorbic acid (AA), uric acid (UA), acetaminophen (AP), pyruvate (PA) and lactate (LA) which shows its potential application in the determination of glucose from human serum samples. The composite film exhibits excellent recovery for glucose in human serum at physiological pH with good practical applicability.     

Study of ITO Glass Electrode Modified with Iron Oxide Nanoparticles and Nafion for Glucose Biosensor Application

In this study, we report the fabrication of the indium tin oxide (ITO) glass electrode modified with iron oxide nanoparticles (IONPs) and nafion for glucose biosensor applications. The IONPs was synthesized using the precipitation method and functionalized with citric acid (CA) to provide hydrophilic surface and functional group for glucose oxidase (GOx) enzyme immobilization. The structural and morphological studies of CA-IONPs were characterized using X-ray diffractometer (XRD) and transmission electron microscope (TEM). The size of the IONPs measured from TEM image was ∼17 nm. The bioelectrode designated as Nafion/GOx/CA-IONPs/ITO was developed by drop casting of the CA-IONPs, GOx and nafion on the ITO glass. The Nafion/GOx/CA-IONPs/ITO bioelectrode showed good electrochemical performance for glucose detection. The functionalized CA-IONPs acted as the catalyst and help to improve the electron transfer rate between GOx and ITO electrode. In addition, thin nafion film was coated on the electrode to prevent interference and improve chemical stability. The Nafion/GOx/CA-IONPs/ITO bioelectrode showed high sensitivity of 70.1 μAmM^-1cm^-2 for the linear range of 1.0-8.0 mM glucose concentrations.     

An electrochemically preanodized screen-printed carbon electrode for achieving direct electron transfer to glucose oxidase

Here we report the unique property of a preanodized screen-printed carbon electrode (SPCE1) that can allow direct electron transfer (DET) reaction of glucose oxidase (GOx). The GOx can be immobilized in the composite of oxygen functionalities and edge plane sites generated during preanodization without additional cross-linking agents. The electron transfer rate of GOx is greatly enhanced to 4.38 s⁻¹ as a result of the conformational change of GOx in the microenvironment enabling the accessibility of active site for GOx to the electrode. The analytical versatility is further improved with the aid of Nafion film. As a consequence, the as-prepared electrode can be used as a glucose biosensor and the number of potential foreign species is then restricted by molecular size, permeation and/or (bio)chemical reaction. Most importantly, the disposable nature of the proposed electrode is expected to promote the DET-related researches.     

MgO polyhedral nanocages and nanocrystals based glucose biosensor

MgO polyhedral nanocages and nanocrystals, synthesized by non-catalytic simple thermal evaporation process, were used to fabricate high-sensitive amperometric glucose biosensor which showed a high and reproducible sensitivity of 31.6 μA μM^?1 cm^?2 with a response time less than 5 s, linear dynamic range from 1.0 to 9.0 μM and correlation coefficient of R = 0.9993. The detection limit of fabricated biosensor (based on S/N ratio = 3) was estimated to be 68.3 ± 0.02 nM. To the best of our knowledge, this is the first report which demonstrates the use of MgO nanostructures for the fabrication of glucose biosensor; hence, this work opens a new way to utilize MgO nanostructures as an efficient electron mediator to fabricate efficient glucose biosensors.     

Synthesis of Au/C and Au/Pani for anode electrodes in glucose microfluidic fuel cell

Gold nanoparticles have been prepared by two methods: chemical (ex-situ, Au/C) by two phase protocol, and electrochemical (in-situ, Au/Pani) by electroreduction of gold ions on a polyaniline film and compared as anode catalysts in a glucose microfluidic fuel cell. In this paper the structural characteristics and electrocatalytic properties were investigated by X-ray diffraction and electrochemical measurements. The catalytic behavior of both anodes was tested in a microfluidic fuel cell with a reference electrode incorporated, by means of linear sweep voltammetry (LSV), showing a cathodic shift in the glucose oxidation peak for Au/Pani. Results show a higher power density (0.5 mW cm^? 2) for Au/C anode compared with an already reported value, where a glucose microfluidic fuel cell was used in similar conditions.     

3-D nanoporous gold thin film for the simultaneous electrochemical determination of dopamine and ascorbic acid

In this study, we demonstrated a novel fabrication method of three dimensional nanoporous gold thin film (NPGF) onto gold (Au) substrate using electrochemical deposition method. Scanning electron microscope (SEM) investigation reveals the formation of highly-ordered pores, approximately 30 nm in diameter and 150 nm thick. The NPGF-modified electrode shows a linear range (0.1–40 μM) for dopamine detection in the presence of ascorbic acid. The electrochemical measurements of mixtures of dopamine, ascorbic acid, and uric acid in human serum sample for real sample applications was also investigated based on differential pulse voltammetry (DPV) technique. These high sensitivity and selectivity features of the proposed NPGF biosensor offer great promise for real sample biosensor application.     

A molecular wire modified glassy carbon electrode for achieving direct electron transfer to native glucose oxidase

Here we describe a strategy for achieving direct electron transfer to native glucose oxidase (GOx), an enzyme in which the redox active centre is buried deep within the glycoprotein. To achieve this a glassy carbon electrode is modified with a mixed monolayer of 4-carboxyphenyl and a 20 Å long oligo(phenylethynyl) molecular wire (MW), assembled from the respective aryl diazonium salts. Subsequently GOx is adsorbed to the interface, followed by covalent attachment. The redox chemistry of the active centre of glucose oxidase, flavin adenine dinucleotide, was observed at an E_1/2 of –443 mV (vs. Ag|AgCl). The enzyme was shown to retain its activity. Most importantly, in the absence of oxygen the electrode was still able to biocatalytically turn over glucose at −400 mV, thereby demonstrating that the enzyme was being recycled back to its catalytically active oxidized form from its inactive reduced form. The rate of enzyme turnover was 1.1 s⁻¹.     

Hydrogen bubble dynamic template synthesis of porous gold for nonenzymatic electrochemical detection of glucose

Gold (Au) films with open interconnected macroporous walls and nanoparticles have been successfully sculptured using the hydrogen bubble dynamic template synthesis followed by a galvanic replacement reaction. Copper (Cu) films with open interconnected macroporous walls and nanoparticles were synthesized using the electrochemically generated hydrogen bubbles as a dynamic template. Then through a galvanic replacement reaction between the porous Cu sacrificial templates and KAu(CN)₂ in solution, the porous Cu films were converted to porous Au films with the similar morphologies. Additional electrochemical dealloying process was introduced to remove the remaining Cu from the porous Au films. X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), Energy-dispersive X-ray (EDX), X-ray diffraction (XRD) and electrochemical methods were adopted to characterize the porous Au films. The resulted porous Au films show excellent catalytic activity toward the electrooxidation of glucose. A nonenzymatic glucose sensor based on those Au film electrodes shows a linear range from 2 to 10 mM with a sensitivity of 11.8 μA cm⁻² mM⁻¹, and a detection limit of 5 μM.     

Gold nanoparticles integrated in a nanotube array for electrochemical detection of glucose

An enzyme-free amperometric glucose sensor of gold nanoparticle-constituted nanotube array electrode is presented. The resulted gold nanotube array electrode with significantly enhanced surface roughness shows prominent catalytic activity toward the electrooxidation of glucose in a pH 7.4 phosphate buffer (PBS) solution and thus can be used to individually or simultaneously determine glucose and the common interfering molecule of ascorbic acid (AA). In the case of glucose detection, the amperometric responses show a linear relationship to glucose concentration in the range of 1 mM–42.5 mM with a detection limit down to 10 μM. The present non-enzymatic glucose electrochemical biosensor shows a good stability and reproducibility.     

Multilayer membranes via layer-by-layer deposition of organic polymer protected Prussian blue nanoparticles and glucose oxidase for glucose biosensing

Polyelectrolyte multilayers (PEMs) are now widely used for bioanalytical applications. In this work, a bilayer of poly(diallydimethylammonium chloride) (PDDA) and poly(sodium 4-styrenesulfonate) (PSS) is consecutively adsorbed on 3-mercapto-1-propanesulfonic acid modified Au electrode surfaces, forming stable, ultrathin multilayer films. Subsequently, Prussian blue nanoparticles protected by PDDA (denoted as P-PB) and negatively charged glucose oxidase (GOx) are consecutively adsorbed onto the PSS-terminated bilayer. The growth of each of the P-PB/GOx bilayers is followed quantitatively using UV-visible absorption spectroscopy and the electrochemical method. The P-PB nanoparticles can catalyze the electroreduction of hydrogen peroxide formed from enzymatic reaction at lower potential and inhibit the responses of interferents, such as ascorbic acid (AA) and uric acid (UA). Performance of the multilayer films can be tailored by controlling the number of bilayers. Under optimal conditions, a linear range of 0.10 to 11.0 mM and a detection limit of 10 microM were achieved. The glucose biosensor has good stability and reproducibility.     

A novel non-enzymatic electrochemical glucose sensor modified with FeOOH nanowire

The recent development in the nanotechnology has paved the way for large number of new materials and devices of desirable properties which have useful functions for electrochemical sensor and biosensor applications. In this paper, a novel enzymeless glucose sensor is developed on the discovery that the FeOOH nanowire in fact possesses an intrinsic enzyme mimetic electrocatalytic activity similar to that found in natural peroxidases. The electrode modified with FeOOH nanowires showed a wide linear range (15 μM–3 mM) and high sensitivity (12.13 μA mM^? 1) for glucose sensing. Other excellent performances such as highly reproducible response, long-term stability, sound mechanical and chemical stability are also observed, and the interferences of ascorbic acid and dopamine can almost be completely avoided. The good analytical performance, low cost and straightforward preparation method made this novel electrode material promising for the development of effective glucose sensors.     

A biosensor prepared by co-entrapment of a glucose oxidase and a carbon nanotube within an electrochemically deposited redox polymer multilayer

A glucose biosensor based on a nanocomposite made by layer-by-layer electrodeposition of the redox polymer into a multilayer containing glucose oxidase (GOx) and single-walled carbon nanotubes (SWCNT) on a screen-printed carbon electrode (SPCE) surface was developed. The objectives of the electrodeposition of redox polymer are to stabilize further the multilayer using a coordinative cross-linked redox polymer and to wire the GOx. The electrochemistry of the layer-by-layer assembly of the GOx/SWCNT/redox polymer nanocomposite was followed by cyclic voltammetry. The resultant biosensor provided stable and reproducible electrocatalytic responses to glucose, and the electrocatalytic current for glucose oxidation was enhanced with an increase in the number of layers. The biosensor displayed a linear range from 0.5 to 6.0mM, a sensitivity of 16.4μA/(mMcm(2)), and a response time of about 5s. It shows no response to 0.05mM of ascorbic acid, 0.32mM of uric acid and 0.20mM of acetaminophen using a Nafion membrane covering the nanocomposite-modified electrode surface.     

Enzymatic glucose biosensor based on flower-shaped copper oxide nanostructures composed of thin nanosheets

Well-crystallized flower-shaped copper oxide nanostructures composed of thin nanosheets has been synthesized by simple low-temperature hydrothermal process and used to fabricate highly sensitive amperometric glucose biosensor which exhibited a high and reproducible sensitivity of 47.19 μA mM^?1 cm^?2, response time less than 5 s, linear dynamic range from 0.01 to 10.0 mM, correlation coefficient of R = 0.9986, and limit of detection (LOD), based on S/N ratio (S/N = 3) of 1.37 μM. This work opens a way to utilize simply-grown CuO nanostructures as an efficient electron mediator to fabricate efficient glucose biosensors.     

Polyelectrolyte adsorption and layer-by-layer assembly: Electrochemical control

Thin films formed via the adsorption or layer-by-layer assembly of charged polymers are important in many sensing, energy, and biomedical applications. When the underlying substrate is a (semi)conductor, the opportunity exists to influence film formation and film properties through an applied electric potential. The recent literature on electrochemical influence of polyelectrolyte-based films is reviewed, with a focus on monolayer and multilayer film assembly and disassembly. Of particular interest are monolayer films grown to a tailored thickness on the 10–100 nm scale, and polyelectrolyte multilayer films controllably disassembled, upon application of a modest electric potential. Experimental observations are discussed in terms of governing factors such as interfacial pH and ionic composition, counter-ion correlations, charge regulation, dielectric discontinuity, and short-range polymer–polymer interactions. Recent modeling efforts are also briefly addressed.     

The process of immobilizing enzyme of glucose sensor based on diamond film

Considering the poor adhesion of electrode to substrate, diamond film as a new kind of substrate material was used to fabricate a glucose sensor. Particularly, the immobilizing enzyme was investigated in detail. SEM and XPS were chosen to identify whether organic functional groups were grafted to electrode surface or not. The response characteristics of a diamond film glucose sensor show that this glucose sensor has good properties in the linear range 0.5–11.4 mM l^-1, sensitivity 4.0 nA mM^-1 mm^-2 and peak reaction speed 2.5 μA. The glucose sensor based on diamond film was a novel microchip glucose sensor with good potential.     

Anodization of Au thin film on Al in oxalic acid

An Au thin film, which was sputter-deposited on an Al substrate, was potentiostatically anodized in oxalic acid. The Au film was first anodized and a spongelike nanoporous film grew down to the interface between Au and Al. Then, the Al was anodized and a very thin and fine nanoporous alumina film was formed underneath the nanoporous Au. Under the same anodization conditions, the current density for Al was ~ 40 μA cm^− 2, less than 1% of that for Au (~ 30 mA cm^− 2). The growth rates of the nanoporous films were ~ 0.7 nm/min for Al and 26 nm/min for Au, indicating that the growth rate of nanoporous alumina was less than 3% of that of nanoporous Au. Al is suitable as the substrate for preparing nanoporous Au films because the electrochemical reactions of both the electrolyte and the substrate are significantly suppressed when the nanopores penetrate Au and the electrolyte reaches the substrate.