Carbon nanotube-chitosan system for electrochemical sensing based on dehydrogenase enzymes

Multiwalled carbon nanotubes (CNT) were solubilized in aqueous solutions of a biopolymer chitosan (CHIT). The CHIT-induced solubilization of CNT facilitated their manipulations, including the modification of electrode surfaces for sensor and biosensor development. The colloidal solutions of CNT-CHIT were placed on the surface of glassy carbon (GC) electrodes to form robust CNT-CHIT films, which facilitated the electrooxidation of NADH. The GC/CNT-CHIT sensor for NADH required approximately 0.3 V less overpotential than the GC electrode. The susceptibility of CHIT to chemical modifications was explored in order to covalently immobilize glucose dehydrogenase (GDH) in the CNT-CHIT films using glutaric dialdehyde (GDI). The stability and sensitivity of the GC/CNT-CHIT-GDI-GDH biosensor allowed for the interference-free determination of glucose in the physiological matrix (urine). In pH 7.40 phosphate buffer solutions, linear least-squares calibration plots over the range 5-300 microM glucose (10 points) had slopes 80 mA M(-1) cm(-2) and a correlation coefficient 0.996. The detection limit was 3 microM glucose (S/N = 3). The CNT-CHIT system represents a simple and functional approach to the integration of dehydrogenases and electrodes, which can provide analytical access to a large group of enzymes for wide range of bioelectrochemical applications including biosensors and biofuel cells.     

Silica‐Mediated Formation of Nickel Sulfide Nanosheets on CNT Films for Versatile Energy Storage

An effective, nondestructive, and universal strategy to homogeneously modify freestanding carbon nanotube (CNT) films with various active species is essential to achieve functional electrodes for flexible electrochemical energy storage, which is challenging and has attracted considerable research interest. In this work, a generalizable concept, to utilize silicon oxide as the intermediate to uniformly decorate various metal sulfide nanostructures throughout CNT films is reported. Taking nickel sulfide nanosheet/CNT (NS/CNT) films, in which the NS nanosheets are homogeneously attached on the intact few‐walled CNTs, as an example, the sheet‐like NS provides sufficient active sites for redox reactions and the CNT network acts as an efficient electron highway, maintaining the structural integrity of the composite and also buffering volume changes. These merits enable NS/CNT films to meet the requirements of versatile energy storage applications. When used for supercapacitors, a high specific capacitance (2699.7 F g^?1/10 A g^?1), outstanding rate performance at extremely high rates (1527 F g^?1/250 A g^?1), remarkable cycling stability, and excellent flexibility can be achieved, among the best performance so far. Moreover, it also delivers excellent performance in the storage of Li and Na ions, meaning it is also potentially suitable for Li/Na ion batteries.     

Preparation, characterization and anion exchange properties of polypyrrole/carbon nanotube nanocomposites

In this study, polypyrrole (PPy) thin films were electrodeposited on carbon nanotube (CNT) backbones by applying a constant deposition potential in 0.1 M pyrrole solution with different electrolytes, such as NaCl, NaNO3, or NaClO4. The hybrid films were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy, and cyclic voltammetry. SEM images revealed the nanostructrure of PPy films generated on CNT surface. The electrochemical and anion exchange properties of the PPy-CNT composite films have been investigated. Nanostructured composite thin films of PPy-CNTs were studied by cyclic voltammetry between 0.4 and -0.8 V in aqueous solution to evaluate their cycling stability and capacity for electrically switched anion exchange. The presence of the CNT backbone greatly improved the anion exchange capacity and stability of the PPy-CNT composite film, which may be attributed to the high surface area of CNT matrix, nanostructure of the PPy film, and the interaction between CNTs and PPy.     

Dioxythiophene-based polymer electrodes for supercapacitor modules

We report on the electrochemical and capacitive behaviors of poly(2,2-dimethyl-3,4-propylene-dioxythipohene) (PProDOT-Me2) films as polymeric electrodes in Type I electrochemical supercapacitors. The supercapacitor device displays robust capacitive charging/discharging behaviors with specific capacitance of 55 F/g, based on 60 μg of PProDOT-Me2 per electrode, that retains over 85% of its storage capacity after 32?000 redox cycles at 78% depth of discharge. Moreover, an appreciable average energy density of 6 Wh/kg has been calculated for the device, along with well-behaved and rapid capacitive responses to 1.0 V between 5 to 500 mV s(-1). Tandem electrochemical supercapacitors were assembled in series, in parallel, and in combinations of the two to widen the operating voltage window and to increase the capacitive currents. Four supercapacitors coupled in series exhibited a 4.0 V charging/discharging window, whereas assembly in parallel displayed a 4-fold increase in capacitance. Combinations of both serial and parallel assembly with six supercapacitors resulted in the extension of voltage to 3 V and a 2-fold increase in capacitive currents. Utilization of bipolar electrodes facilitated the encapsulation of tandem supercapacitors as individual, flexible, and lightweight supercapacitor modules.     

Electropolymerized flavin adenine dinucleotide as an advanced NADH transducer

Electropolymerizing the prosthetic group (flavin adenine dinucleotide, FAD) responsible in the active sites of dehydrogenases for NAD(+)|NADH regeneration, we succeeded in mimicking enzyme activity. Poly(FAD) characterized by an additional polymer-type redox reaction has been discovered as a highly effective electrocatalyst for NADH oxidation: operating at the lowest potentials reported for NADH transducers (0.00 V, pH 7.4), poly(FAD) is characterized by the electrochemical rate constant of 1.8 +/- 0.6 x 10(-3) cm s(-1), which is at the level of the NADH mass-transfer constant. Flow injection analysis of NADH with the poly(FAD)-modified wall-jet electrode as a detector has been characterized by a linear calibration range prolonged down to 5 x 10(-7) M and a sensitivity of 0.08 A M(-1) cm(-2), which taking into account the dispersion coefficient ( approximately 3), is at the diffusion-limiting value. In contrast to the low molecular weight mediators able to exhibit similar electrocatalytic properties, poly(FAD)-modified electrodes are characterized by the dramatically improved stability and, thus, can be considered as the most advantageous NADH transducers for analytical chemistry.     

Carbon nanotube/teflon composite electrochemical sensors and biosensors

The fabrication and attractive performance of carbon nanotube (CNT)/Teflon composite electrodes, based on the dispersion of CNT within a Teflon binder, are described. The resulting CNT/Teflon material brings new capabilities for electrochemical devices by combining the advantages of CNT and "bulk" composite electrodes. The electrocatalytic properties of CNT are not impaired by their association with the Teflon binder. The marked electrocatalytic activity toward hydrogen peroxide and NADH permits effective low-potential amperometric biosensing of glucose and ethanol, respectively, in connection with the incorporation of glucose oxidase and alcohol dehydrogenase/NAD(+) within the three-dimensional CNT/Teflon matrix. The accelerated electron transfer is coupled with minimization of surface fouling and surface renewability. These advantages of CNT-based composite devices are illustrated from comparison to their graphite/Teflon counterparts. The influence of the CNT loading upon the amperometric and voltammetric data, as well as the electrode resistance, is examined. SEM images offer insights into the nature of the CNT/Teflon surface. The preparation of CNT/Teflon composites overcomes a major obstacle for creating CNT-based biosensing devices and expands the scope of CNT-based electrochemical devices.     

Oxygen Evolution Assisted Fabrication of Highly Loaded Carbon Nanotube/MnO2 Hybrid Films for High‐Performance Flexible Pseudosupercapacitors

To date, it has been a great challenge to design high‐performance flexible energy storage devices for sufficient loading of redox species in the electrode assemblies, with well‐maintained mechanical robustness and enhanced electron/ionic transport during charge/discharge cycles. An electrochemical activation strategy is demonstrated for the facile regeneration of carbon nanotube (CNT) film prepared via floating catalyst chemical vapor deposition strategy into a flexible, robust, and highly conductive hydrogel‐like film, which is promising as electrode matrix for efficient loading of redox species and the fabrication of high‐performance flexible pseudosupercapacitors. The strong and conductive CNT films can be effectively expanded and activated by electrochemical anodic oxygen evolution reaction, presenting greatly enhanced internal space and surface wettability with well‐maintained strength, flexibility, and conductivity. The as‐formed hydrogel‐like film is quite favorable for electrochemical deposition of manganese dioxide (MnO₂) with loading mass up to 93 wt% and electrode capacitance kept around 300 F g^?1 (areal capacitance of 1.2 F cm^?2). This hybrid film was further used to assemble a flexible symmetric pseudosupercapacitor without using any other current collectors and conductive additives. The assembled flexible supercapacitors exhibited good rate performance, with the areal capacitance of more than 300 mF cm^?2, much superior to other reported MnO₂ based flexible thin‐film supercapacitors.     

Insulin oxidation and determination at carbon electrodes

The redox chemistry of insulin was investigated at glassy carbon (GC) electrodes that were coated with films of chitosan (CHIT) and multiwalled carbon nanotubes (CNT). While bare electrodes deactivated quickly during insulin oxidation, the GC electrodes coated with CHIT and CHIT-CNT films generated stable insulin currents. The GC/CHIT-CNT electrodes were used for investigating the electrooxidation process of insulin and amperometric determination of insulin. The mass spectrometric, electron paramagnetic resonance, and separation studies of electrolyzed insulin solutions suggested that the loss of 4 mass units upon insulin oxidation at CNT could be accounted for by the formation of two dityrosine cross-links intramolecularly. At a potential of 0.700 V and physiological pH 7.40, the GC/CHIT-CNT electrodes displayed a detection limit of approximately 30 nM insulin (S/N = 3), sensitivity of 135 mA M(-1) cm(-2), linear dynamic range from 0.10 to 3.0 microM (R2 = 0.995), and superior operational and long-term stability. The CNT-based electrodes are promising new insulin detectors for diabetes-related studies such as fast chromatographic analysis of therapeutic insulin formulations or evaluation of quality of pancreatic islets prior to their transplantation.     

Use of the electrochromic behaviour of lanthanide phthalocyanine films for nicotinamide adenine dinucleotide detection

Electrochromic properties of spun films of bis[octakis(hexylthio)phthalocyaninato] dysprosium(III) were investigated for determining nicotinamide adenine dinucleotide hydride (NADH) in water solutions. A spin-coated film deposited on indium tin oxide electrode displays only one redox couple (at E1/2=0.78V). The films of [(C6H13S)8Pc]2Dy were modified chemically or electrochemically for the detection of reduced NADH in water solution. The modified film in the oxidized ([(C6H13S)8Pc]2Dy)+ form is believed to be reduced to its neutral form on interaction with NADH.     

Glucose biosensor based on carbon nanotube epoxy composites

A novel glucose biosensor based on a rigid and renewable carbon nanotube (CNT) based biocomposite is reported. The biosensor was based on the immobilization of glucose oxidase (GOx) within the CNT epoxy-composite matrix prepared by dispersion of multi-wall CNT inside the epoxy resin. The use of CNT, as the conductive part of the composite, ensures better incorporation of enzyme into the epoxy matrix and faster electron transfer rates between the enzyme and the transducer. Experimental results show that the CNT epoxy composite biosensor (GOx-CNTEC) offers an excellent sensitivity, reliable calibration profile, and stable electrochemical properties together with significantly lower detection potential (+0.55 V) than GOx-graphite epoxy composites (+0.90 V; difference deltaE = 0.35 V). The results obtained favorably compare to those of a glucose biosensor based on a graphite epoxy composite (GOx-GEC).     

Use of polymeric indicator for electrochemical DNA sensors: poly(4-vinylpyridine) derivative bearing [Os(5,6-dimethyl-1,10-phenanthroline)2Cl]2+

A poly(4-vinylpyridine) (PVP) derivative bearing redox-active osmium complexes, PVP-[Os(5,6-dmphen)(2)Cl](2+) (5,6-dmphen = 5,6-dimethyl-1,10-phenanthroline), was employed as a hybridization indicator for electrochemical DNA sensors. PVP-[Os(5,6-dmphen)(2)Cl](2+) exhibited approximately 1000 times higher sensitivity than the corresponding monomeric analogue, [Os(5,6-dmphen)(3)](2+), in DNA determination due to polymeric effects. The detection limit of the present sensor was approximately 0.5 amol. Another merit of the polymeric indicator is that the redox potential was found to be +360 mV (vs Ag/AgCl), which is significantly lower than that reported for the monomeric analogue (+672 mV). The polymeric indicator was applicable to the discrimination of single- and double-base-mismatched DNAs from fully matched target DNA. The polymeric indicator can be removed from the electrode surface by rinsing the electrode in a high-temperature buffer for 6 min, and thus, the polymeric indicator-based DNA sensor can be used repeatedly.     

A numerical study on carbon nanotube pullout to understand its bridging effect in carbon nanotube reinforced composites

Carbon nanotube (CNT) reinforced polymeric composites provide a promising future in structural engineering. To understand the bridging effect of CNT in the events of the fracture of CNT reinforced composites, the finite element method was applied to simulate a single CNT pullout from a polymeric matrix using cohesive zone modelling. The numerical results indicate that the debonding force during the CNT pullout increases almost linearly with the interfacial crack initiation shear stress. Specific pullout energy increases with the CNT embedded length, while it is independent of the CNT radius. In addition, a saturated debonding force exists corresponding to a critical CNT embedded length. A parametric study shows that a higher saturated debonding force can be achieved if the CNT has a larger radius or if the CNT/matrix has a stronger interfacial bonding. The critical CNT embedded length decreases with the increase of the interfacial crack initiation shear stress.     

Carbon nanotube wiring: a tool for straightforward electrochemical biosensing at magnetic particles

Here, we combine the unique properties of carbon nanotubes (CNTs) and magnetic particles (MPs) to develop a novel biosensing approach for the specific detection of electroactive labels and targets. The assay is based on label/target capture and concentration using MPs. It follows addition of CNTs, which adsorb onto the surface of the beads. The subsequent magnetic entrapment of the CNT/MP complexes onto an electrode allows straightforward electrochemical sensing of the MP surface by exploiting CNT wiring. As a proof of concept, the assay has been applied to detection of ferrocene labels, and to the specific immunodetection of dopamine in both artificial saline solutions and real sample matrixes. The results demonstrate the applicability of CNT as wiring tools for enzymeless and substrateless electrochemical biosensing.     

Electrochemical biosensor based on integrated assembly of dehydrogenase enzymes and gold nanoparticles

Development of a highly sensitive nanostructured electrochemical biosensor based on the integrated assembly of dehydrogenase enzymes and gold (Au) nanoparticle is described. The Au nanoparticles (AuNPs) have been self-assembled on a thiol-terminated, sol-gel-derived, 3-D, silicate network and enlarged by hydroxylamine seeding. The AuNPs on the silicate network efficiently catalyze the oxidation of NADH with a decrease in overpotential of approximately 915 mV in the absence of any redox mediator. The surface oxides of AuNP function as an excellent mediator, and a special inverted "V" shape voltammogram at less positive potential was observed for the oxidation of NADH. The AuNP self-assembled sol-gel network behaves like a nanoelectrode ensemble. The nanostructured electrode shows high sensitivity (0.056 +/- 0.001 nA/nM) toward NADH with an amperometric detection limit of 5 nM. The electrode displays excellent operational and storage stability. A novel methodology for the fabrication of a NADH-dependent dehydrogenase biosensor based on the integration of dehydrogenase enzyme and AuNPs with the silicate network is developed. The enzymatically generated NADH is, in turn, electrocatalytically detected by the AuNPs on the silicate network. The integrated assembly has been successfully used for the amperometric biosensing of lactate and ethanol at a potential of -5 mV. The biosensor is very stable and highly sensitive, and it has a fast response time. The excellent performance validates the integrated assembly as an attractive sensing element for the development of new dehydrogenase biosensors.     

Amperometric biosensors based on redox polymer-carbon nanotube-enzyme composites

Based on their size and unique electrical properties, carbon nanotubes offer the exciting possibility of developing ultrasensitive, electrochemical biosensors. In this study, we describe the construction of amperometric biosensors based on the incorporation of single-walled carbon nanotubes modified with enzyme into redox polymer hydrogels. The composite films were constructed by first incubating an enzyme in a single-walled carbon nanotube (SWNTs) solution and then cross-linking within a poly[(vinylpyridine)Os(bipyridyl)(2)Cl(2+/3+)] polymer film. Incorporation of SWNTs, modified with glucose oxidase, into the redox polymer films resulted in a 2-10-fold increase in the oxidation and reduction peak currents during cyclic voltammetry, while the glucose electrooxidation current was increased 3-fold to approximately 1 mA/cm(2) for glucose sensors. Similar effects were also observed when SWNTs were modified with horseradish peroxidase prior to incorporation into redox hydrogels.     

Electrochemistry and electrocatalytic properties of hemoglobin in layer-by-layer films of SiO2 with vapor-surface sol-gel deposition

In this paper, layer-by-layer {Hb/SiO2}n films assembled by alternate adsorption of positively charged hemoglobin (Hb) and vapor-surface sol-gel deposition of silica at 50 degrees C onto a glassy carbon electrode were reported. The result films were characterized with cyclic voltametery, electrochemical impedance spectroscopy, UV-vis spectroscopy, and SEM, and the direct electrochemical and electrocatalytic properties of Hb in these layer-by-layer films were investigated. A pair of well-defined quasi-reversible cyclic voltammetric peaks were observed, and the formal potential of the heme FeIII/FeII redox couple was found to be -0.330 V(vs SCE). The electron-transfer behavior of Hb in {Hb/SiO2}n films was dependent on the vapor temperature, the number of layers, and the pH of the Hb solution, based on which a set of optimized conditions for film fabrication was inferred. The hemoglobin in{Hb/SiO2}n films displayed good electrocatalytic activity to the reduction of hydrogen peroxide, and H2O2 had linear current response from 1.0 x 10(-6) to 2.0 x 10(-4) M with a detection limit of 5.0 x 10(-7) M (S/N = 3). The apparent heterogeneous electron-transfer rate constant (ks) was 1.02 +/- 0.03 s(-1), and the apparent Michaeli-Menten constant (Kmapp) was 0.155 mM, indicating a potential application in the third-generation biosensor.     

Preparation and characterisation of titanium dioxide films for catalytic applications generated by anodic spark deposition

The advanced plasma electrochemical process of anodic spark deposition (ASD) was used to generate photoactive titanium dioxide films on titanium metal substrates. A shift to easier-to-machine substrates was demonstrated by the deposition of a titanium film with physical vapour deposition onto different materials such as glass, silicon, and stainless steel prior to ASD. Obtained films were characterised by scanning electron microscopy, surface area measurement (Brunnauer-Emmett-Teller method, BET), X-ray diffraction, electron-probe microanalysis, and glow discharge spectroscopy. Additionally, film thickness was determined by eddy current measurements. Standard ASD conditions were defined as 180 V applied voltage over a 180 s hold time, a voltage ramp of 20 V/s, a duty cycle of 0.5 and a frequency of 1500 Hz. Most prominent characteristics of the titanium films produced under these standard conditions are a film thickness of ≤80 μm, a surface area of approximately 51 m²/g (BET) and an anatase content of approximately 30% and rutile content of approximately 70%. Furthermore, the film formation process is elucidated and the dependence of film thickness on deposition time and the dependence of the anatase and rutile content on the deposited mass are shown for varying ASD conditions.     

Bioinorganic composites for enzyme electrodes

Sparingly soluble redox salts were combined with a model enzyme, glucose oxidase, in a host matrix of a biopolymer chitosan to form bioinorganic composite films on the surface of glassy carbon electrodes. Four redox salts, each containing the Ru(NH3)6(3+) cation and a selected anion, such as Ru(CN)6(4-), Fe(CN)6(4-), Co(CN)6(3-) or IrCl6(3-), were studied. The composition and catalytic properties of such composite materials toward glucose oxidation were investigated by spectroscopic and electrochemical methods. The composite films provided an oxygen-independent electrical communication between the enzyme's redox centers and a glassy carbon surface at a potential as low as -0.10 V vs Ag/AgCl(3 M Cl-). The nature of the electrical communication is discussed in terms of redox mediation by the Ru(NH3)6(3+)-containing ion pairs formed inside the biocomposites. The kinetic significance of the mediator's charge is considered by postulating that neutral ion pairs are more efficient redox mediators of the enzymatic reaction than those negatively charged. The low operating potential of enzyme electrodes based on the bioinorganic composites allows for an interference-free determination of glucose. The design of the biocomposites is generic and can incorporate oxidoreductase enzymes other than glucose oxidase to provide a host of biosensors for biologically and environmentally important analytes.     

A facile synthesis of α-Ni(OH)2-CNT composite films for supercapacitor application

The α-Ni(OH)₂-CNT composite films have been successfully synthesized by a simple chemical method and their supercapacitive properties were investigated by variation of CNT. The structural, compositional, morphological, wettability and electrochemical properties of the composite films were studied by using various characterization techniques. X-ray diffraction analysis revealed that the synthesized composite films are polycrystalline in nature. FT-Raman spectroscopy result showed the characteristic Raman band of CNT and α-Ni(OH)₂ which confirmed the formation of α-Ni(OH)₂-CNT composite. SEM micrographs showed porous microstructure of the synthesized films and hydrophilic nature of the films was confirmed from wettability studies. Furthermore, the effect of the variation of CNT on the electrochemical properties of the synthesized composite films was discussed. The electrochemical performance of the composite films was studied by using cyclic voltammetry (CV) and Galvanostatic charge–discharge (GCD) techniques. The α-Ni(OH)₂-CNT composite showed highest specific capacitance of 544 F g^?1 with high retention capability of 85% after 1500th cycle and excellent cycling stability.     

紫外-可见光谱分析碳纳米管电泳液浓度对阴极场发射性能的影响

将酸化的碳纳米管(CNT)粉末、硝酸镁置于异丙醇溶剂中超声处理,制备成分散均匀的CNT电泳液.采用不同CNT浓度的电泳液在CrCuCr电极上电泳沉积CNT薄膜,并对阴极样品进行场发射性能测试;同时采用紫外-可见光谱仪对CNT电泳液进行光谱分析.结果表明,CNT浓度为0~0.13 g/L的电泳液在258 nm处存在光谱吸收,且其吸光度与相应CNT浓度呈良好的线性关系;当CNT浓度为0.12 g/L时电泳沉积制备的CNT阴极场发射性能较好,其开启电场为0.903 V/μm,当电场强度为1.395 V/μm时场发射电流密度为2.903 mA/cm2.利用紫外-可见光谱可以有效地分析电泳液中CNT浓度,为电泳沉积良好质量的CNT薄膜提供了保证.