Nanobioelectroanalysis Based on Carbon/Inorganic Hybrid Nanoarchitectures

The emergence of nanotechnology has opened new horizons for electrochemical biosensors. This review highlights new concepts for electrochemical biosensors based on different carbon/inorganic hybrid nanoarchitectures. Particular attention will be given to hybrid nanostructures involving 1‐ or 2‐dimensional carbon nanotubes or graphene along with inorganic nanoparticles (gold, platinum, quantum dot (QD), metal oxide). Latest advances (from 2007 onwards) in electrochemical biosensors based on such hybrids of carbon/inorganic‐nanomaterial heterostructures are discussed and illustrated in connection to enzyme electrodes for blood glucose or immunoassays of cancer markers. Several strategies for using carbon/inorganic nanohybrids in such bioaffinity and biocatalytic sensing are described, including the use of hybrid nanostructures for tagging or modifying electrode transducers, use of inorganic nanomaterials as surface modifiers along with carbon nanomaterial label carriers, and carbon nanostructure‐based electrode transducers along with inorganic amplification tags. The implications of these nanoscale bioconjugated hybrid materials on the development of modern electrochemical biosensors are discussed along with future prospects and challenges.     

A Review on the Effects of Introducing CNTs in the Modification Process of Electrochemical Sensors

This review summarizes some developments in the fabrication of modified sensors and biosensors through the incorporating the carbon nanotubes (CNTs) in their modification ingredients. A large number of papers have paid attention towards the application of carbon nanotubes (CNTs) as electrode constituents and studied its electrochemical behavior. Here, we survey the achievements in the detection of various substances with high selectivity and sensitivity provided using CNTs based electrodes. Moreover, modified electrodes by CNTs have demonstrated the electrocatalytic features and higher sensitivity in detection of analytes. The improved characteristics arises from the large surface area and good conductivity of CNTs. However, it should be considered that the use of single walled carbon nanotubes (SWCNTs) or multi‐walled carbon nanotubes (MWCNTs), the presence of impurities, and the chemical procedures adopted are effective on the performance of the modified sensors.     

Carbon‐Nanotube Based Electrochemical Biosensors: A Review

This review addresses recent advances in carbon‐nanotubes (CNT) based electrochemical biosensors. The unique chemical and physical properties of CNT have paved the way to new and improved sensing devices, in general, and electrochemical biosensors, in particular. CNT‐based electrochemical transducers offer substantial improvements in the performance of amperometric enzyme electrodes, immunosensors and nucleic‐acid sensing devices. The greatly enhanced electrochemical reactivity of hydrogen peroxide and NADH at CNT‐modified electrodes makes these nanomaterials extremely attractive for numerous oxidase‐ and dehydrogenase‐based amperometric biosensors. Aligned CNT “forests” can act as molecular wires to allow efficient electron transfer between the underlying electrode and the redox centers of enzymes. Bioaffinity devices utilizing enzyme tags can greatly benefit from the enhanced response of the biocatalytic‐reaction product at the CNT transducer and from CNT amplification platforms carrying multiple tags. Common designs of CNT‐based biosensors are discussed, along with practical examples of such devices. The successful realization of CNT‐based biosensors requires proper control of their chemical and physical properties, as well as their functionalization and surface immobilization.     

Use of nanomaterials for impedimetric DNA sensors: A review

This review presents the state of the art of DNA sensors (or genosensors) that utilize electrochemical impedance spectroscopy as the transduction technique. As issue of current interest, it is centered on the use of nanomaterials to develop or to improve performance of these specific biosensors. It will describe the different principles that may be employed in the measuring step and the different formats adopted for detection of a DNA sequence or confirmation or amplification of the finally obtained signal. The use of nanomaterials for the above listed aspects, viz. the use of carbon nanotubes or other nanoscopic elements in the construction of the electrodes, or the use of nanoparticles, mainly gold or quantum dots, for signal enhancement will be fully revised.     

Electrochemical sensors and biosensors based on redox polymer/carbon nanotube modified electrodes: A review

The aim of this review is to present the contributions to the development of electrochemical sensors and biosensors based on polyphenazine or polytriphenylmethane redox polymers together with carbon nanotubes (CNT) during recent years. Phenazine polymers have been widely used in analytical applications due to their inherent charge transport properties and electrocatalytic effects. At the same time, since the first report on a CNT-based sensor, their application in the electroanalytical chemistry field has demonstrated that the unique structure and properties of CNT are ideal for the design of electrochemical (bio)sensors. We describe here that the specific combination of phenazine/triphenylmethane polymers with CNT leads to an improved performance of the resulting sensing devices, because of their complementary electrical, electrochemical and mechanical properties, and also due to synergistic effects. The preparation of polymer/CNT modified electrodes will be presented together with their electrochemical and surface characterization, with emphasis on the contribution of each component on the overall properties of the modified electrodes. Their importance in analytical chemistry is demonstrated by the numerous applications based on polymer/CNT-driven electrocatalytic effects, and their analytical performance as (bio) sensors is discussed.     

基于碳纳米管的化学修饰电极及电化学生物传感器的研究进展

综述了碳纳米管的结构、合成、纯化、功能化、分散及基于碳纳米管的化学修饰电极和电化学生物传感器的研究进展。     

碳纳米管在电化学和光化学纳米生物传感器中的应用

碳纳米管(CNTs)因具有独特的物理化学及电化学性质,如较大的比表面积、较强的电子转移能力和良好的吸附性能等而引起人们的广泛关注.碳纳米管可以通过物理吸附、静电或疏水作用等非共价结合方式或共价连接方式固定生物大分子(如蛋白质、DNA、抗体等),有效地促进生物大分子与电极间直接、快速的电子转移,可应用于多种电化学生物传感器中.碳纳米管本身在近红外光区具有独特的荧光和拉曼光谱,可以利用多种光谱手段对多种生物分子实现定量检测,因此近年来碳纳米管在光化学生物传感器中的应用也逐渐受到了研究者的重视.本文对碳纳米管在电化学和光化学生物传感器中的应用进行了简要综述和展望.     

Immobilization of Acetylcholinesterase onto Carbon Nanotubes Utilizing Streptavidin-biotin Interaction for the Construction of Amperometric Biosensors for Pesticides

Abstract

Carbon nanotubes (CNTs) are very promising materials onto which bioactive molecules can be immobilized in the construction of biosensors. Streptavidin was used as a molecular linker to immobilize biotinylated acetylcholinesterase (AChE) on CNTs in a gentle and controllable fashion for pesticide biosensors. Glassy carbon electrodes coated with the CNT-enzyme complex had high affinity for the substrate acetylthiocholine and produced strong peak oxidation currents in electrochemical assays. We also propose a new method, i.e., the use of relative net slope rather than the percentage of inhibition, in the calculation of pesticide concentrations. The biosensors could detect low levels of the pesticide methyl paraoxon.     

Electrochemical Biosensing for Cancer Cells Based on TiO2/CNT Nanocomposites Modified Electrodes

Both TiO₂ nanoparticles and carbon nanotubes have been usually utilized to modify the electrodes to enhance the detection sensitivity of biomolecular recognition. In this research, novel TiO₂/CNT nanocomposites have been prepared and doped on the carbon paper as the modified electrodes. Subsequently, the redox behavior of the ferricyanide probe and the surface properties of the cancer cells coated on the modified electrodes have been investigated by using electrochemical and contact angle measurements. Compared with electrochemical signals on bare carbon paper and nanocomposite modified substrates, the significantly enhanced electrochemical signals on the modified electrodes covered with cancer cells have been observed. Meanwhile, different leukemia cells (i.e., K562/ADM cells and K562/B.W. cells) could be also recognized because of their different electrochemical behavior and hydrophilic/hydrophobic features on the modified electrodes due to the specific components on the plasma membranes of the target cells. This new strategy may have potential application in the development of the biocompatible and multi‐signal responsive biosensors for the early diagnosis of cancers.     

Carbon nanofiber vs. carbon microparticles as modifiers of glassy carbon and gold electrodes applied in electrochemical sensing of NADH

Carbon materials (CMs), such as carbon nanotubes (CNTs), carbon nanofibers (CNFs), and carbon microparticles (CMPs) are used as doping materials for electrochemical sensors. The efficiency of these materials (either before or after acidic treatments) while being used as electrocatalysts in electrochemical sensors is discussed for β-nicotinamide adenine dinucleotide (NADH) detection using cyclic voltammetry (CV). The sensitivity of the electrodes (glassy carbon (GC) and gold (Au)) modified with both treated and untreated materials have been deeply studied. The response efficiencies of the GC and Au electrodes modified with CNF and CMP, using dimethylformamide (DMF) as dispersing agent are significantly different due to the peculiar physical and chemical characteristics of each doping material. Several differences between the electrocatalytic activities of CMs modified electrodes upon NADH oxidation have been observed. The CNF film promotes better the electron transfer of NADH minimizing the oxidation potential at +0.352 V. Moreover higher currents for the NADH oxidation peak have been observed for these electrodes. The shown differences in the electrochemical reactivities of CNF and CMP modified electrodes should be with interest for future applications in biosensors.     

New CNT/poly(brilliant green) and CNT/poly(3,4-ethylenedioxythiophene) based electrochemical enzyme biosensors

A combination of the electroactive polymer poly(brilliant green) (PBG) or conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) with carbon nanotubes to obtain CNT/PBG and CNT/PEDOT modified carbon film electrodes (CFE) has been investigated as a new biosensor platform, incorporating the enzymes glucose oxidase (GOx) as test enzyme, alcohol oxidase (AlcOx) or alcohol dehydrogenase (AlcDH). The sensing parameters were optimized for all biosensors based on CNT/PBG/CFE, CNT/PEDOT/CFE platforms. Under optimized conditions, both GOx biosensors exhibited very similar sensitivities, while in the case of AlcOx and AlcDH biosensors, AlcOx/CNT/PBG/CFE was found to give a higher sensitivity and lower detection limit. The influence of dissolved O₂ on oxidase-biosensor performance was investigated and was shown to be different for each enzyme. Comparisons were made with similar reported biosensors, showing the advantages of the new biosensors, and excellent selectivity against potential interferents was successfully demonstrated. Finally, alcohol biosensors were successfully used for the determination of ethanol in alcoholic beverages.     

Carbon nanotube/polysulfone composite screen-printed electrochemical enzyme biosensors

The fabrication, evaluation and attractive performance of multiwall carbon nanotube(MWCNT)/polysulfone biocomposite membrane modified thick-film screen-printed electrochemical biosensors are reported. The fabricated carbon nanotube/polysulfone (CNT/PS) strips combine the attractive advantages of carbon nanotube materials, polysulfone matrix and disposable screen-printed electrodes. Such thick-film carbon nanotubes/polysulfone sensors have a well defined performance, are mechanically stable, and exhibit high electrochemical activity. Furthermore, biocompatibility of CNT/PS composite allows easy incorporation of biological functional moiety of horseradish peroxidase by phase inversion technique. The comparison of graphite with MWCNT as conductor material is described in this paper. The proposed H(2)O(2) biosensor exhibited a linear range (applied potential, -0.2 V) from 0.02 to 0.5 mM and a K(M)(app) of 0.71 mM.     

The advantage of using carbon nanotubes compared with edge plane pyrolytic graphite as an electrode material for oxidase-based biosensors

Carbon nanotubes (CNTs) are promising materials for use in amperometric biosensors. The defect sites at their ends, and on their sidewalls, are considered to be edge plane-like defects and show high electrocatalytic activity toward several biological molecules. However, electrocatalytic activity toward H(2)O(2) has not been compared among bamboo-structured CNTs (BCNTs), which have many defect sites; hollow-structured CNTs (HCNTs), which have few defect sites; edge plane pyrolytic graphite (EPG); and traditional glassy carbon (GC). The advantages of using CNTs in electrodes for biosensors are still equivocal. To confirm the utility of CNTs, we analyzed the electrochemical performance of these four carbon electrodes. The slope of the calibration curve for H(2)O(2) at potentials of both +0.6 V and -0.1 V obtained with a BCNT paste electrode (BCNTPE) was more than 10 times greater than the slopes obtained with an HCNT paste electrode and a GC electrode, reflecting the BCNT's larger number of defect sites. Although the slope with the EPG electrode (EPGE) was about 40 times greater than that with BCNTPE at +0.6 V, the slopes with these two carbon electrodes were nearly equivalent at -0.1 V. EPGE demonstrated excessive electrochemical activity, detecting currents on the basis of consumption of oxygen and oxidation of ascorbic acid, even at -0.1 V. In contrast, BCNTPE could dominantly detect a cathodic current for H(2)O(2) at -0.1 V, even when interfering molecules were added. BCNTPE possesses appropriate electrochemical activity and is an effective electrode materials for developing interference-free oxidase-based biosensors operated by the application of an appropriate potential.     

Demonstration of the advantages of using bamboo-like nanotubes for electrochemical biosensor applications compared with single walled carbon nanotubes

The modification of glassy carbon electrodes with random dispersions of nanotubes is currently the most popular approach to the preparation of carbon nanotube modified electrodes. The performance of glassy carbon electrodes modified with a random dispersion of bamboo type carbon nanotubes was compared with single walled carbon nanotubes modified glassy carbon electrodes and bare glassy carbon electrodes. The electrochemical performance of all three types for electrode were compared by investigating the electrochemistry with solution species and the oxidation of guanine and adenine bases of surface adsorbed DNA. The presence of edge planes of graphene at regular intervals along the walls of the bamboo nanotubes resulted in superior electrochemical performance relative to SWNT modified electrodes from two aspects. Firstly, with solution species the peak separation of the oxidation and reduction waves were smaller indicating more rapid rates of electron transfer. Secondly, a greater number of electroactive sites along the walls of the bamboo-carbon nanotubes (BCNTs) resulted in larger current signals and a broader dynamic range for the oxidation of DNA bases.     

Electrochemical Biosensing Systems Based on Carbon Nanotubes and Carbon Nanofibers

Abstract

Carbon nanomaterials are in the forefront of research in a variety of chemical and physical disciplines. Of these, certain nanostructures seem to be suitable for the development of electrochemical biosensors. In particular carbon nanotubes, and carbon nanofibers have specific chemical and physical characteristics that lent them ideal for the development of biosensors with unique analytical characteristics. In particular, their conductivity, surface area, inherent and induced chemical functionalities, and biocompatibility provide the grounds for the development of a new era of electrochemical biosensors. In this review, we will examine the recent developments of biosensor design based on these new nanostructures.     

Carbon Nanomaterials in Biosensors: Should You Use Nanotubes or Graphene?

From diagnosis of life‐threatening diseases to detection of biological agents in warfare or terrorist attacks, biosensors are becoming a critical part of modern life. Many recent biosensors have incorporated carbon nanotubes as sensing elements, while a growing body of work has begun to do the same with the emergent nanomaterial graphene, which is effectively an unrolled nanotube. With this widespread use of carbon nanomaterials in biosensors, it is timely to assess how this trend is contributing to the science and applications of biosensors. This Review explores these issues by presenting the latest advances in electrochemical, electrical, and optical biosensors that use carbon nanotubes and graphene, and critically compares the performance of the two carbon allotropes in this application. Ultimately, carbon nanomaterials, although still to meet key challenges in fabrication and handling, have a bright future as biosensors.     

Bio-electrocatalysis of NADH and ethanol based on graphene sheets modified electrodes

Characterization and application of graphene sheets modified glassy carbon electrodes (graphene/GC) have been presented for the electrochemical bio-sensing. A probe molecule, potassium ferricyanide is employed to study the electrochemical response at the graphene/GC electrode, which shows better electron transfer than graphite modified (graphite/GC) and bare glassy carbon (GC) electrodes. Based on the highly enhanced electrochemical activity of NADH, alcohol dehydrogenase (ADH) is immobilized on the graphene modified electrode and displays a more desirable analytical performance in the detection of ethanol, compared with graphite/GC or GC based bio-electrodes. It also exhibits good performance of ethanol detection in the real samples. From the results of electrochemical investigation, graphene sheets with a favorable electrochemical activity could be an advanced carbon electrode materials for the design of electrochemical sensors and biosensors.     

基于新型纳米传感材料的DNA生物传感器的应用

DNA是构建纳米技术和生物传感技术新设备的良好构建体.DNA生物传感器由于具有灵敏度高、选择性好等特点,近年来获得了飞速发展.研究发现,金属纳米粒子(MNPs)、碳基纳米材料等一系列纳米材料在传感器设计中提高了电化学DNA传感器的传感性能.本文侧重介绍了场效应晶体管、石墨烯、碳纳米管等新型纳米传感材料,以及基于这些材料...     

Electrochemistry of polystyrene intercalated vertically aligned single- and double-walled carbon nanotubes on gold electrodes

Electrochemical electrodes incorporating double- and single-walled carbon nanotubes (CNTs) were fabricated on cysteamine modified flat gold substrates. Through covalent coupling of the amine end groups with carboxyl functionalized CNTs, a dense forest of vertically aligned CNTs was produced. To these a 30 nm thick insulating polystyrene layer was spin coated, resulting in exposure of the uppermost carbon nanotube ends. The electrochemical performance of each electrode was then determined using the redox probe ruthenium hexaamine. Once surrounded by polymer, the double-walled CNTs (DWCNTs) showed an improved electron transfer rate, compared to the single-walled electrode. This improvement was attributed to the protection of the electronic properties of the inner wall of the DWCNT during the chemical modification and suggests that DWCNTs may offer a useful alternative to SWCNTs in future electrochemical sensors and biosensors.     

纳米碳管作为氧扩散电极催化层第二相碳载体的电极特性

A novel gas diffusion electrode using binary carbon supports (carbon nanotubes and active carbon) as the catalyst layer was prepared. The electrochemical properties for oxygen reduction reaction (ORR) in alkaline electrolyte were investigated by polarization curves and electrochemical impedance spectroscopy. The results show that the binary-support electrode exhibits higher electrocatalytic activity than the single-support electrode, and the best performance is obtained when the mass ratio of carbon nanotubes and activated carbon is 50 ∶50. The results from their electrode kinetic parameters indicate that the introduction of carbon nanotubes as a secondary support provides high accessible surface area, good electronic conductivity and fast ORR kinetics. The electrocatalytic activity of binary-support electrodes is obviously improved by the deposition of Pt nanoparticles on carbon nanotubes, even at very low Pt loading (45.7 μg/cm2). In addition, the EIS analysis results show that the process of ORR may be controlled by diffusion of oxygen in the thin film for binary-support electrodes with or without Pt catalyst.