Microwave plasma treated carbon nanotubes and their electrochemical biosensing application

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

Functionalized carbon nanotubes and nanofibers for biosensing applications

This review summarizes recent advances in electrochemical biosensors based on carbon nanotubes (CNTs) and carbon nanofibers (CNFs) with an emphasis on applications of CNTs. CNTs and CNFs have unique electric, electrocatalytic and mechanical properties, which make them efficient materials for developing electrochemical biosensors.We discuss functionalizing CNTs for biosensors. We review electrochemical biosensors based on CNTs and their various applications (e.g., measurement of small biological molecules and environmental pollutants, detection of DNA, and immunosensing of disease biomarkers). Moreover, we outline the development of electrochemical biosensors based on CNFs and their applications. Finally, we discuss some future applications of CNTs.     

Electrochemical DNA biosensors based on platinum nanoparticles combined carbon nanotubes

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

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.     

The use of electrochemical impedance spectroscopy for biosensing

This review introduces the basic concepts and terms associated with impedance and techniques of measuring impedance. The focus of this review is on the application of this transduction method for sensing purposes. Examples of its use in combination with enzymes, antibodies, DNA and with cells will be described. Important fields of application include immune and nucleic acid analysis. Special attention is devoted to the various electrode design and amplification schemes developed for sensitivity enhancement. Electrolyte insulator semiconductor (EIS) structures will be treated separately. Figure An alternating current which is forced to pass an interface is sensitive to surface changes and will detect impedance changes due to biomolecule immobilisation or formation of a recognition complex. This can be used for the construction of biosensor electrodes     

Biosensors based on carbon nanotubes

Carbon nanotubes (CNTs) exhibit a unique combination of excellent mechanical, electrical and electrochemical properties, which has stimulated increasing interest in the application of CNTs as components in (bio)sensors. This review highlights various design methodologies for CNT-based biosensors and their employment for the detection of a number of biomolecules. In addition, recent developments in the fields of CNT-based chemiresistors and chemically sensitive field-effect transistors are presented. After a critical discussion of the factors that currently limit the practical use of CNT-based biosensors, the review concludes with an outline of potential future applications for CNTs in biology and medicine.      

纳米金、碳纳米管和纳米线及其在电化学生物传感器研究中的应用

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

Improved Detection Limit and Stability of Amperometric Carbon Nanotube-Based Immunosensors by Crosslinking Antibodies with Polylysine

Amperometric immunosensor configurations featuring covalently bound anti-biotin antibodies (Ab) embedded into a polylysine (PLL)-single walled carbon nanotube (SWCNT) composite layer were evaluated. Assemblies were made by first oxidizing pyrolytic graphite (PG) electrodes to form surface carboxylic acid groups, to which PLL, SWCNTs and anti-biotin were covalently linked. Incorporating SWCNT into PLL-antibody assemblies improved the amperometric detection limit for biotin (Ag) labeled with horseradish peroxidase to 10 fmol mL(-1). Anti-biotin embedded into the PLL matrix had improved thermal stability and retained its binding ability for biotin after exposure to temperatures of 42 degrees C for up to 3 hours, while the noncrosslinked antibody was inactivated at this temperature in several minutes.     

Carbon nanotubes as separation carrier in capillary electrophoresis

The utility and versatility of carboxylic single-walled carbon nanotubes (c-SWNT) in capillary electrophoresis (CE) is demonstrated, using as model solutes homologues and structural isomers. In the case of homologues of caffeine and theobromine, distinct changes in the electrophoretic parameters occur at a critical concentration of c-SWNT in the run buffer. It is suggested that the c-SWNT of a definite concentration could form a network in the run buffer as a pseudostationary phase on the basis of the unique tubule structure, providing a different separation from sodium dodecyl sulfate (SDS) micelles. In the case of structural isomers of catechol and hydroquinone, differing from the homologues, it is mainly attributable to the functional groups on the c-SWNT that have an effect on the electrophoretic behaviors by forming intermolecular hydrogen bonding with analytes. Furthermore, aggregated c-SWNT serve as anticonvective media and minimize solute diffusion contributing to zone broadening. The presence of charged c-SWNT suppressed the electrodiffusion and decreased the adsorption between capillary wall and solutes, which led to better peak shapes of isomers.     

Carbon nanotubes: Solid-phase extraction

Since the first report in 1991, carbon nanotubes (CNTs) have shown great possibilities for a wide variety of processes and applications, which include their use as electrodes, sensors (gas, enzymatic, etc.), nanoprobes, electronic materials, field emitters, etc. The combination of structures, dimensions and topologies has provided physical and chemical attractive properties that are unparalleled by most known materials. Their applications have also reached the Analytical Chemistry field in which CNTs are being used as matrices in matrix assisted laser desorption ionization, stationary phases in either gas chromatography, high performance liquid chromatography or capillary electrochromatography, also as pseudostationary phases in capillary electrophoresis, etc. as well as new solid-phase extraction (SPE) materials. Concerning this last application the number of works has considerably increased in the last five years. This review article pretends to focus on the most important features and different applications of SPE using CNTs (including matrix solid-phase dispersion and solid-phase microextraction) covering articles published since their introduction up to now (September 2009).     

Electrochemical DNA Biosensors Based on Palladium Nanoparticles Combined with Carbon Nanotubes

Palladium nanoparticles, in combination with multi‐walled carbon nanotubes (MWCNTs), were used to fabricate a sensitivity‐enhanced electrochemical DNA biosensor. MWCNTs and palladium nanoparticles were dispersed in Nafion, which were used to modify a glassy carbon electrode (GCE). Oligonucleotides with amino groups at the 5′ end were covalently linked onto carboxylic groups of MWCNTs on the electrode. The hybridization events were monitored by differential pulse voltammetry (DPV) measurement using methylene blue (MB) as an indicator. Due to the ability of carbon nanotubes to promote electron‐transfer and the high catalytic activities of palladium nanoparticles for electrochemical reaction of MB, the sensitivity of presented electrochemical DNA biosensors was remarkably improved. The detection limit of the method for target DNA was 1.2×10^?13 M.     

Cu2+-doped polypyrrole nanotubes with promoted efficiency for peroxidase mimicking and electrochemical biosensing

A facile template together with doping strategy is presented to fabricate Cu²⁺-doped polypyrrole (Cu²⁺/PPy) nanotubes (NTs) as efficient mimicking peroxidase and electrocatalyst. PPy NTs were first prepared using electrospun polyacrylonitrile nanofibers as templates and subsequently doped with Cu²⁺ via a simple immersion strategy. The as-prepared Cu²⁺/PPy NTs not only exhibit an outstanding peroxidase-like catalytic efficiency but also possess an excellent electrocatalytic activity, which is used for the detection of glucose, displaying a great promise for biosensing applications. The good enzyme-like and electrochemical performances of Cu²⁺/PPy NTs are owing to the reduced Fermi level compared with bare PPy NTs, which is beneficial for promoting the electron transfer to the substrate. The novel Cu²⁺/PPy NTs are a novel type of enzyme mimics and electrocatalysts for potential bright applications in biotechnology and environment science.     

An Electrochemical Immunosensor for C‐Reactive Protein Based on Multi‐Walled Carbon Nanotube‐Modified Electrodes

C‐reactive protein (CRP) is a nonspecific biomarker of inflammation and infection that can be used as a predictive risk marker of cardiovascular disease in asymptomatic individuals or as a prognostic marker of recurrent ischemia and death among patients with coronary heart disease or stroke. We developed a sensitive, disposable, and easy to operate sensor based on heterogeneous sandwich immunoassay for high sensitivity CRP (hs‐CRP) measurement. We used screen‐printed electrodes modified with multi‐walled carbon nanotubes and protein A to ensure the oriented immobilization of anti‐CRP antibodies. CRP was quantitatively measured down to a concentration of 0.5 ng mL^?1, enabling high dilution of the samples before measurement and consequently reducing interferences present in the serum. The sensor developed is suitable for point of care detection of hs‐CRP at clinically relevant concentrations for the diagnosis of both conventional and low‐grade inflammations.     

DNA‐Directed Attachment of Carbon Nanotubes for Enhanced Label‐Free Electrochemical Detection of DNA Hybridization

Multi‐walled carbon nanotubes (MWNTs) were used as nanowires, which combined DNA molecules to a carbon paste electrode (CPE). The attachment of MWNT on the electrode surface was controlled by a hybridization assay between adenine and thymine containing oligonucleotides. The appearance of guanine oxidation signal after hybridization with target DNA greatly simplified the specific sequence DNA detection mechanism. Combination of sidewall‐ and end‐functionalization of MWNT provided a significant enhancement in the voltammetric signal of guanine oxidation in comparison with the signals obtained from only end‐oxidized MWNT modified CPE and a bare CPE. A control experiment involving adenine containing polynucleotide (poly(A)) instead of adenine probe modified MWNT was performed. The effect of target and noncomplementary DNA concentration on the guanine signal was also monitored. Discrimination against single‐base mismatch and noncomplementary DNA was achieved by surfactant containing washing solution. The promising conductivity of carbon nanotubes, and the creation of a larger surface area for DNA immobilization by sidewall‐ and end‐oxidation of MWNT provided a detection limit down to 10 pg/mL, which is compatible with the demand of the genetic tests.     

Polymerized ionic liquid-wrapped carbon nanotubes: The promising composites for direct electrochemistry and biosensing of redox protein

Polymerized ionic liquid-wrapped carbon nanotubes (PIL-CNTs) were firstly designed for direct electrochemistry and biosensing of redox proteins. The CNTs were coated successfully with polymerized ionic liquid (PIL) layer, as verified by transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and Fourier transform infrared (FT-IR) spectroscopy. The PIL-CNTs were dispersed better in water and showed superior electrocatalysis toward O₂ and H₂O₂ comparing to pristine CNTs and the mixture of IL monomer and CNTs. With glucose oxidase (GOD) as a protein model, the direct electrochemistry of the redox protein was investigated on the PIL-CNTs modified glassy carbon (GC) electrode and excellent direct electrochemical performance of GOD molecules was observed. The proposed biosensor (GOD/PIL-CNTs/GC electrode) displayed good analytical performance for glucose with linear response up to 6 mM, response sensitivity of 0.853 μA mM⁻¹, good stability and selectivity.     

A New Application of Carbon Nanotubes Constructing Biosensor

Carbon nanotubes used for constructing biosensor was described for the first time. Single-wall carbon nanotubes (SWNTs) functionalized with carboxylic acid groups were used to immobilize glucose oxidase forming a glucose biosensor. The biosensor response can be determined by amperometric method at a low applied potential (0.40V).     

Carbon nanotube transistors for biosensing applications

Electronic detection of biomolecules, although still in its early stages, is gradually emerging as an effective alternative to optical detection methods. We describe field effect transistor devices with carbon nanotube conducting channels that have been developed and used for biosensing and biodetection. Both transistors with single carbon nanotube conducting channels and devices with nanotube network conducting channels have been fabricated and their electronic characteristics examined. The devices readily respond to changes in the environment, and such effects have been examined using gas molecules and coatings with specific properties. Device operation in (conducting) buffer and in a dry environment--after buffer removal--is also discussed. Applications in the biosensing area are illustrated with three examples: the investigation of the interaction between devices and biomolecules, the electronic monitoring of biomolecular processes, and attempts to integrate cell membranes with active electronic devices.     

Study of the nonenzymatic glucose sensor based on highly dispersed Pt nanoparticles supported on carbon nanotubes

An amperometric biosensor for sensitive and selective detection of glucose has been constructed by using highly dispersed Pt nanoparticles supported on carbon nanotubes (Pt-MWCNTs) as sensing interface. The Pt-MWCNTs were synthesized by using the two-step pyrolysis method. This composite shows good electrocatalytic activity towards the oxidation of glucose in alkaline and thus can be used to selectively detect glucose. We found that detection potential and Nafion amount covered on the Pt-MWCNTs modified glassy carbon electrode had considerable influence on the selectivity for amperometric detection of glucose. Under optimal detection conditions (detection potential of 0.0 V versus SCE and 10 μL 1.5% Nafion), selective detection of glucose in the glucose concentration range of 1.0-26.5 mM (correlation coefficient, >0.999) can be performed. The results demonstrate that the Pt-MWCNTs composite is promising for the fabrication of nonenzymatic glucose sensors.     

Synthesis and electrochemical characterization of carbon nanotubes decorated with nickel nanoparticles for use as an electrochemical capacitor

Attachment of nickel nanoparticles on multiwalled carbon nanotubes (MWCNTs) was conducted to explore the influence of Ni loading on the electrochemical capacitance of MWCNT electrodes. A chemical impregnation leaded to homogeneously disperse Ni particles onto the surface of MWCNTs, and the Ni particles were found to be an average size of 30–50 nm. The capacitive behavior of the MWCNT electrodes was investigated in 6 M KOH, by using cyclic voltammetry (CV), charge–discharge cycling, and ac electrochemical impedance spectroscopy. CV measurements showed that the Faradaic current was found to increase with the Ni coverage, indicating that the presence of Ni would enhance the pseudocapacitance through the redox process. Equivalent circuit analysis indicated that both of electrical connection and charge transfer resistances accounted for the major proportion of the overall resistance and were found to decrease with the amount of nickel. A linearity relationship between the total capacitance and the Ni population reflected that each Ni particle exhibits an identical electrochemical activity in enhancing the electrochemical capacitance. The overall electrochemical capacitance (including double layer capacitance and pseudocapacitance) of Ni-MWCNT electrode can reach a maximum of 210 F/g over 500 cycles.     

Comparative studies on electrochemical activity of graphene nanosheets and carbon nanotubes

This study compares the electrochemical activity of four kinds of carbon materials, i.e. single-walled carbon nanotubes (SWNTs), pristine graphene oxide nanosheets (GONs), chemically reduced GONs, and electrochemically reduced GONs, with potassium ferricyanide (K₃Fe(CN)₆), β-nicotinamide adenine dinucleotide (NADH) and ascorbic acid (AA) as the redox probes. Cyclic voltammetry (CV) results demonstrate that the electron transfer kinetics of the redox probes employed here at the carbon materials essentially depend on the kind of the materials, of which the redox processes of the probes at SWNTs and electrochemically reduced GONs are faster than those at the pristine and chemically reduced GONs. The different electron transfer kinetics for the redox probes at the carbon materials studied here could be possibly ascribed to the synergetic effects of the surface chemistry (e.g., C/O ratio, presence of quinone-like groups, surface charge, and surface cleanness) and conductivity of the materials. This study could be potentially useful for understanding the structure/property relationship of the carbon materials and, based on this, for screening and synthesizing advanced carbon materials for electrochemical applications.