Glassy Carbon Electrodes Modified with Multiwall Carbon Nanotubes Dispersed in Polylysine

We report the analytical performance of glassy carbon electrodes (GCE) modified with a dispersion of multiwall carbon nanotubes (MWCNT) in polylysine (Plys) (GCE/MWCNT‐Plys). The resulting electrodes show an excellent electrocatalytic activity towards different bioanalytes like ascorbic acid, uric acid and hydrogen peroxide, with important decrease in their oxidation overvoltages. The dispersion of 1.0 mg/mL MWCNT in 1.0 mg/mL polylysine is highly stable, since after 2 weeks the sensitivity for hydrogen peroxide at GCE modified with this dispersion remained in a 90% of the original value. The MWCNT‐Plys layer immobilized on glassy carbon electrodes has been also used as a platform to build supramolecular architectures by self‐assembling of polyelectrolytes based on the polycationic nature of the polylysine used to disperse the nanotubes. The self‐assembling of glucose oxidase has allowed us to obtain a supramolecular multistructure for glucose biosensing. The influence of glucose oxidase concentration and adsorption time as well as the effect of using polylysine or MWCNT‐Plys as polycationic layers for further adsorption of GOx is also evaluated.     

Adsorption and Electrooxidation of Nucleic Acids at Glassy Carbon Electrodes Modified with Multiwalled Carbon Nanotubes Dispersed In Polylysine

We report the advantages of the adsorption and electrooxidation of oligonucleotides and calf‐thymus double stranded DNA (dsDNA) at glassy carbon electrodes (GCE) modified with a dispersion of multiwalled carbon nanotubes (MWCNT) in poly‐L ‐lysine (Plys) (GCE/MWCNT‐Plys). Important enhancement in the guanine oxidation signal was obtained by adsorptive stripping voltammetry (AdSV) due to a most favorable interaction between the negatively charged DNAs and the positively charged Plys that support the MWCNT. The layer of oligo(dG)₁₁ immobilized at GCE/MWCNT‐Plys was successfully used for the selective detection of the hybridization event using oligo(dG)₁₁/oligo(dC)₁₁ as model.     

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.     

Electrochemical Sensor for the Quantification of Dopamine Using Glassy Carbon Electrodes Modified with Single‐Wall Carbon Nanotubes Covalently Functionalized with Polylysine

We report a dopamine electrochemical sensor based on the modification of glassy carbon electrodes (GCE) with polylysine‐functionalized single‐wall carbon nanotubes (SWCNT‐PLys). The resulting electrodes (GCE/SWCNT‐PLys) showed a significant improvement in the electrooxidation of dopamine with drastic decrease in the peak potentials separation and important enhancement in the associated currents. Dopamine was detected by differential pulse voltammetry‐adsorptive stripping with medium exchange at nanomolar levels even in the presence of high excess of ascorbic and uric acids. The sensor was successfully used for the quantification of dopamine in urine samples enriched with the neurotransmitter.     

Electrochemical Sensing of Ascorbic Acid,Hydrogen Peroxide and Glucose by Bimetallic (Fe,Ni)−CNTs Composite Modified Electrode

In this research, bimetallic supported CNT modified electrode ( Fe,Ni/CNTs/GCE) has been developed for sensitive, stable and highly elctroactive sensing of glucose, ascorbic acid and hydrogen peroxide. Transition metals such as Iron (Fe) and Nickel (Ni) offer high electrical and thermal conductance, high active surface‐to‐volume ratio and presence of d‐band electrons gives enhanced electrocatalytic behavior. While, CNTs provide high surface area, stability and excellent conductivity. Synthesized material is characterized by SEM, EDS, XRD and FTIR to access morphology, elemental composition and structure. This unique combination is employed for the electrochemical sensing of ascorbic acid, glucose and hydrogen peroxide and different experimental parameters are optimized. Fe,Ni/CNTs/GCE shows good sensing efficiency at pH 7.4 which is ideally suitable for variety of analytes. The modified electrode also show good reproducibility and sensitivity under optimized conditions and can be reused upto 30 cycles without compromising the efficiency. With good linearity, reproducibility and limit of detection, this material possess significant potential as non‐enzymatic biosensor for variety of analytes.     

Electron-transfer properties of different carbon nanotube materials,and their use in glucose biosensors

Different types of carbon nanotube material (single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs) of different internal diameter) have been used for preparation of CNT-modified glassy-carbon electrodes. Redox reactions involving ferricyanide and hydrogen peroxide were examined at the CNT-modified electrodes. Electrodes modified with SWCNTs usually had better electron-transfer properties than MWCNT-modified electrodes. Glucose biosensors were also prepared with electropolymerized polyphenylenediamine films, CNT materials, and glucose oxidase. Amperometric behavior in glucose determination was examined. SWCNT-modified glucose biosensors usually had a wider dynamic range (from 0.1 to 5.5 mmol L⁻¹) and greater sensitivity in glucose determination. The detection limit was estimated to be 0.05 mmol L⁻¹.     

Characterization and Electrocatalytic Activity of Nanocomposites Consisting of Nanosized Cobalt Tetraaminophenoxy Phthalocyanine,Multi‐walled Carbon Nanotubes and Gold Nanoparticles

Glassy carbon electrodes were modified with composites containing cobalt tetraaminophenoxy phthalocyanine nanoparticles (CoTAPhPc NP ), multi‐walled carbon nanotubes (MWCNT) and gold nanorods (AuNRs). The modified electrodes were studied for their electrocatalytic behavior towards the reduction of hydrogen peroxide. Phthalocyanine nanoparticles significantly improved electron transfer kinetics as compared to phthalocyanines which are not in the nanoparticle form when alone or in the presence of multiwalled carbon nanotubes (MWCNTs). CoTAPhPc NP ‐MWCNT‐GCE proved to be suitable for hydrogen peroxide detection with a catalytic rate constant of 3.45×10³ M^?1 s^?1 and a detection limit of 1.61×10^?7 M. Adsorption Gibbs free energy ΔG^o was found to be ?19.22 kJ mol^?1 for CoTAPhPc NP ‐MWCNT‐GCE.     

Dispersion of multi-wall carbon nanotubes in polyethylenimine: A new alternative for preparing electrochemical sensors

In this work we report on the analytical performance of glassy carbon electrodes modified with a dispersion of multi-wall carbon nanotubes in polyethylenimine (GCE/(PEI/CNT)). The resulting electrodes show an excellent electrocatalytic activity toward different bioanalytes like ascorbic acid, dopamine, 3,4-dihydroxyphenylacetic acid (dopac) and hydrogen peroxide. An important decrease in the overvoltages for the oxidation of ascorbic acid (505 mV) and hydrogen peroxide (350 mV) and for the reduction of hydrogen peroxide (450 mV), as well as a dramatic improvement in the reversibility of the electrochemical behavior of dopamine and dopac is obtained. The currents are higher than those obtained with other dispersant agents like Nafion, concentrated acids or chitosan, evidencing the high efficiency of the dispersion in PEI. The GCE/(PEI/CNT) demonstrated to be highly reproducible, with 3.0% RSD for the sensitivity of hydrogen peroxide for 10 electrodes prepared with five different dispersions. Differences in sensitivity of 10.0% were obtained for hydrogen peroxide with electrodes prepared using the same dispersion even after 14 days preparation. The CNT/PEI layer immobilized on glassy carbon electrodes has been also used as a platform for building supramolecular architectures based on the self-assembling of polyelectrolytes without any pretreatment of the electrode surface, oxidation or derivatization of the carbon nanotubes, just taking advantages of the polycationic nature of the polymer used for dispersing the nanotubes. The self-assembling of glucose oxidase has allowed us to obtain a supramolecular multistructure for glucose biosensing, with detection limits of 11 μM (0.02 g/L). Such an excellent performance of GCE/(PEI/CNT) toward hydrogen peroxide and the effectiveness of the use of CNT/PEI as a platform for obtaining supramolecular multistructures, represents a very good alternative for developing other enzymatic biosensors.     

Ordered Mesoporous Carbon Paste Electrodes for Electrochemical Sensing and Biosensing

Surface renewable ordered mesoporous carbon paste electrodes (OMCPE) were prepared by mechanical mixing ordered mesoporous carbon (OMC) and mineral oil. Electrochemical behavior of the composite electrode was evaluated and compared with the conventional graphite paste (GPE) and carbon nanotubes paste (CNTPE) electrodes. The OMCPE provided improved electron transfer kinetics and catalytic capabilities in connection with oxidation and/or reduction of different redox systems, such as ferricyanide and some biological species, e. g. ascorbic acid (AA), uric acid (UA), β‐nicotinamide adenine dinucleotide (NADH), dopamine (DA), epinephrine (EP), acetaminophenol (AP) and hydrogen peroxide. The substantial decrease in the over voltage of the hydrogen peroxide oxidation along with the facile incorporation of glucose oxidase (GOD) into the composite matrix allowed us successfully to fabricate a sensitive and selective glucose biosensor. A linear response up to 15 mM glucose was obtained for the OMCPE modified with 10% GOD (w/w) with a detection limit of 0.072 mM. In addition, we also successfully applied the OMCPE to the anodic stripping voltammetric analysis of heavy metal ions with improved sensitivities in comparison with CNTPE and GPE. The excellent experimental results implicate that the new developed paste electrode holds great promise in the design of electrochemical devices, such as sensors and biosensors.     

Hybrid Materials from Carbon Nanotubes,Nickel Tetrasulfonated Phthalocyanine and Thin Polymer Layers for the Selective Electrochemical Activation of Nitric Oxide in Solution

The elaboration of hybrid materials from single‐wall carbon nanotubes (SWCNT) and tetrasulfonated nickel phthalocyanine (NiTSPc) was electrochemically performed to obtain chemically modified electrodes with improved electrocatalytic activity towards the electrooxidation of nitric oxide (NO). The characterization of these hybrid electrodes was achieved by cyclic voltammetry and AFM. The electrochemical performances of the electrodes towards the oxidation of NO were then analyzed by chronoamperometry and the obtained results show that the presence of SWCNT greatly enhances the electrocatalytic performances in terms of current intensity. Additional coatings were then electrodeposited over the hybrid electrodes to act as selective membranes against four major interfering analytes: nitrite, ascorbate, hydrogen peroxide and L ‐arginine. Several polymer coatings were tested to achieve the best balance between sensitivity to NO and selectivity against interferents.     

Bioanalytical Application of the Ordered Mesoporous Carbon Modified Electrodes

An ordered mesoporous carbon modified electrode (OMCE) was prepared by film forming method. The electrochemical behavior of the OMCE was evaluated in connection with the electrochemistry of some electroactive biospecies, such as ascorbic acid (AA), acetaminophenol (AP), cysteine (CySH), dopamine (DA), epinephrine (EP), uric acid (UA), β‐nicotinamide adenine dinucleotide (reduced disodium salt hydrate, NADH), and hydrogen peroxide (H₂O₂) with cyclic voltammetry. Compared with the conventional carbon nanotubes (CNT) and graphite powder (GP) modified electrodes, the OMCE provided the best electrochemical reactivities in all cases associated with decreased over potential, better‐defined peak shape, and higher sensitivity. In addition, the OMC, CNT, and GP modified electrodes were employed as sensitive sensors for H₂O₂ and NADH quantification and as stable platforms for the fabrication of glucose and ethanol biosensors on which the enzymes were immobilized.     

Amperometric Glucose Biosensors Based on Glassy Carbon and SWCNT‐Modified Glassy Carbon Electrodes

Different carbonaceous materials, such as single‐walled carbon nanotubes (SWCNTs) and glassy carbon submitted to an electrochemical activation at +1.80 V (vs. SCE) for 900 s, have been used with the aim of comparing their performances in the development of enzyme electrodes. Commercial SWCNTs have been pretreated with 2.2 M HNO₃ for 20 h prior to use. The utility of activated GC as promising material for amperometric oxidase‐based biosensors has been confirmed. With glucose oxidase (GOx) as a model enzyme, glucose was efficiently detected up to 1 mM without the use of a mediator. Both electrodes operated in stirred solutions of 0.1 M phosphate buffer (pH 5.5), containing dissolved oxygen, at a potential of ?0.40 V vs. SCE. Although the performances of the two carbonaceous materials were comparable, the biosensors based on activated GC were characterized by a practically unchanged response 40 days after the fabrication, a better signal to noise ratio, and a little worse sensitivity. In addition, the preparation procedure of such biosensors was more simple, rapid and reproducible.     

Amperometric Glucose Biosensors Based on Integration of Glucose Oxidase onto Prussian Blue/Carbon Nanotubes Nanocomposite Electrodes

Nanosized Prussian blue (PB) particles were synthesized with a chemical reduction method and then the PB nanoparticles were assembled on the surface of multiwall carbon nanotubes modified glassy carbon electrode (PB/MWNTs/GCE). The results showed that the PB/MWNTs nanocomposite exhibits a remarkably improved catalytic activity towards the reduction of hydrogen peroxide. Glucose oxidase (GOD) was immobilized on the PB/MWNTs platform by an electrochemically polymerized o‐phenylenediamine (OPD) film to construct an amperometric glucose biosensor. The biosensor exhibited a wide linear response up to 8 mM with a low detection limit of 12.7 μM (S/N=3). The Michaelis–Menten constant K_m and the maximum current i_max of the biosensor were 18.0 mM and 4.68 μA, respectively. The selectivity and stability of the biosensor were also investigated.     

Investigation of the Effect of Different Glassy Carbon Materials on the Performance of Prussian Blue Based Sensors for Hydrogen Peroxide

Three different kinds of glassy carbon (GC‐R, GC‐K, GC‐G) were equally pretreated, further modified with electrochemically deposited Prussian Blue and used as sensors for hydrogen peroxide at an applied potential of ?50 mV (vs. Ag|AgCl). Their performance was evaluated with respect to the following parameters: the coverage and electrochemistry of the electrodeposited Prussian Blue, the sensitivity and the lower limit of detection for hydrogen peroxide, and the operational stability of the sensors. GC‐R showed the best behavior concerning the surface coverage and the operational stability of the electrodeposited Prussian Blue. For this electrode the sensitivity for hydrogen peroxide (10 μM) was 0.25 A/M cm² and the detection limit was 0.1 μM. Scanning electron microscopy was used to study the surfaces of the three electrodes before and after the electrodeposition of Prussian Blue and to search for the reason for the three different behaviors between the different glassy carbon materials. The Prussian Blue modified GC‐R was also used for the construction of a glucose biosensor based on immobilizing glucose oxidase in Nafion membranes on top of electrodeposited Prussian Blue layer. The operational stability of the glucose biosensors was studied in the flow injection mode at an applied potential of ?50 mV (vs. Ag|AgCl) and alternatively injecting standard solutions of hydrogen peroxide (10 μM) and glucose (1 mM) for 3 h. For the GC‐R based biosensor a 2.8% decrease of the initial glucose response was observed.     

Electropolymerized Diphenylamine on Functionalized Multiwalled Carbon Nanotube Composite Film and Its Application to Develop a Multifunctional Biosensor

Diphenylamine (DPA) monomers have been electropolymerized on the amino‐functionalized multiwalled carbon nanotube (AFCNT) composite film modified glassy carbon electrode (GCE) by cyclic voltammetry (CV). The surface morphology of PDPA‐AFCNT was studied using field‐emission scanning electron microscopy (FE‐SEM). The interfacial electron transfer phenomenon at the modified electrode was studied using electrochemical impedance spectroscopy (EIS). The PDPA‐AFCNT/GCE represented a multifunctional sensor and showed good electrocatalytic behavior towards the oxidation of catechol and the reduction of hydrogen peroxide. Rotating‐disk electrode technique was applied to detect catechol with a sensitivity of 1360 µA mM^?1 cm^?2 and a detection limit of 0.01 mM. Amperometric determination of hydrogen peroxide at the PDPA‐AFCNT film modified electrode results in a linear range from 10 to 800 µM, a sensitivity of 487.1 µA mM^?1 cm^?2 and detection limit of 1 µM. These results show that the nano‐composite film modified electrode can be utilized to develop a multifunctional sensor.     

MWCNTs/Ionic Liquid/Graphene Quantum Dots Nanocomposite Coated with Nickel‐Cobalt Bimetallic Catalyst as a Highly Selective Non‐enzymatic Sensor for Determination of Glucose

In this work, a glassy carbon electrode (GCE) was modified with multiwall carbon nanotubes/ionic liquid/graphene quantum dots (MWCNTs/IL/GQDs) nanocomposite. Then, the nanocomposite was decorated with nickel‐cobalt nanoparticles (Ni?Co NPs), and it was used as a non‐enzymatic glucose sensor. Field emission scanning electron microscopy, X‐ray diffraction spectroscopy, and energy dispersive spectroscopy were employed to prove the electrodeposition of the Ni?Co NPs on the surface of MWCNTs/IL/GQDs/GCE. Also, cyclic voltammetric and amperometric methods were utilized for the investigation of the electrochemical behaviour of the Ni?Co NPs/MWCNTs/IL/GQDs/GCE for glucose oxidation. The novel amperometric sensor displayed two linear ranges from 1.0 to 190.0 μmol L^?1 and 190.0 to 4910 μmol L^?1 with a low detection limit of 0.3 μmol L^?1 as well as fast response time (2 s) and high stability. Also, the sensor showed good selectivity for glucose determination in the presence of ascorbic acid, citric acid, dopamine, uric acid, fructose, and sucrose, as potential interference species. Finally, the performance of the proposed sensor was investigated for the glucose determination in real samples. Ni?Co NPs/MWCNTs/IL/GQDs/GCE showed good sensitivity and excellent selectivity.     

Integrated, electrically contacted NAD(P)+-dependent enzyme-carbon nanotube electrodes for biosensors and biofuel cell applications

Integrated, electrically contacted beta-nicotinamide adenine dinucleotide- (NAD(+)) or beta-nicotinamide adenine dinucleotide phosphate- (NADP(+)) dependent enzyme electrodes were prepared on single-walled carbon nanotube (SWCNT) supports. The SWCNTs were functionalized with Nile Blue (1), and the cofactors NADP(+) and NAD(+) were linked to 1 through a phenyl boronic acid ligand. The affinity complexes of glucose dehydrogenase (GDH) with the NADP(+) cofactor or alcohol dehydrogenase (AlcDH) with the NAD(+) cofactor were crosslinked with glutaric dialdehyde and the biomolecule-functionalized SWCNT materials were deposited on glassy carbon electrodes. The integrated enzyme electrodes revealed bioelectrocatalytic activities, and they acted as amperometric electrodes for the analysis of glucose or ethanol. The bioelectrocatalytic response of the systems originated from the biocatalyzed oxidation of the respective substrates by the enzyme with the concomitant generation of NAD(P)H cofactors. The electrocatalytically mediated oxidation of NAD(P)H by 1 led to amperometric responses in the system. Similarly, an electrically contacted bilirubin oxidase (BOD)-SWCNT electrode was prepared by the deposition of BOD onto the SWCNTs and the subsequent crosslinking of the BOD units using glutaric dialdehyde. The BOD-SWCNT electrode revealed bioelectrocatalytic functions for the reduction of O(2) to H(2)O. The different electrically contacted SWCNT-based enzyme electrodes were used to construct biofuel cell elements. The electrically contacted GDH-SWCNT electrode was used as the anode for the oxidation of the glucose fuel in conjunction with the BOD-SWCNT electrode in the presence of O(2), which acted as an oxidizer in the system. The power output of the cell was 23 muW cm(-2). Similarly, the AlcDH-SWCNT electrode was used as the anode for the oxidation of ethanol, which was acting as the fuel, with the BOD-SWCNT electrode as the cathode for the reduction of O(2). The power output of the system was 48 microW cm(-2).     

Electrocatalytic Activity of Bamboo‐Structured Carbon Nanotubes Paste Electrode Toward Hydrogen Peroxide

Abstract

In this report, we describe the finding that bamboo‐structured carbon nanotubes (CNT) showed superior electrocatalytic activity toward hydrogen peroxide. The slope of the calibration curve for hydrogen peroxide obtained with the bamboo‐structured CNT paste electrode was more than 20 times as large as the slopes obtained with hollow‐structured CNT paste and glassy carbon electrodes at an operating potential of ?0.1 V, with no interfering reactions. Incorporation of glucose oxidase within the bamboo‐structured CNT paste electrode allows the selective detection of glucose in the presence of common interferents without using any permselective membranes. This excellent ability of the bamboo‐structured CNT paste electrode toward hydrogen peroxide is applicable to the development of other enzymatic biosensors.     

Adsorption and Electrooxidation of DNA at Glassy Carbon Electrodes Modified with Multiwall Carbon Nanotubes Dispersed in Glucose Oxidase

We are proposing for the first time the successful immobilization of DNA at glassy carbon electrodes (GCE) modified with carbon nanotubes (CNT) dispersed in glucose oxidase (GOx) (GCE/CNT‐GOx) either by direct adsorption or by layer‐by‐layer self‐assembling using polydiallyldimethylamine (PDDA). The presence of GOx allows an efficient dispersion of CNT and gives a most favorable environment that promotes the adsorption and makes possible a more sensitive electrooxidation of DNA. The PDDA incorporated in the self‐assembled architecture largely facilitates the adsorption and electrooxidation of dsDNA and the adsorbed layer can be successfully used for evaluating the interaction of DNA with methylene blue.     

Hydrogen Peroxide Sensor Based on Carbon Nanotubes/β‐Ni(OH)2 Nanocomposites

Ni(OH)₂ nanoflowers were synthesized by a simple and energy‐efficient wet chemistry method. The product was characterized by scanning electron microscopy (SEM) and X‐ray powder diffraction (XRD). Then Ni(OH)₂ nanoflowers attached multi‐walled carbon nanotubes (MWCNTs) modified glassy carbon electrodes (GCE) were proposed (MWCNTs/Ni(OH)₂/GCE) to use as electrochemical sensor to detect hydrogen peroxide. The results showed that the synergistic effect was obtained on the MWCNTs/Ni(OH)₂/GCE whose sensitivity was better than that of Ni(OH)₂/GCE. The linear range is from 0.2 to 22 mmol/L, the detection limit is 0.066 mmol/L, and the response time is <5 s. Satisfyingly, the MWCNTs/Ni(OH)₂/GCE was not only successfully employed to eliminate the interferences from uric acid (UA), acid ascorbic (AA), dopamine (DA), glucose (GO) but also NO₂^? during the detection. The MWCNTs/Ni(OH)₂/GCE allows highly sensitive, excellently selective and fast amperometric sensing of hydrogen peroxide and thus is promising for the future development of hydrogen peroxide sensors.