Electrocatalytic detection of insulin at RuOx/carbon nanotube-modified carbon electrodes

A bilayer surface coating, prepared by electrodepositing ruthenium oxide (RuOx) onto a carbon nanotube (CNT) layer, offers dramatic improvements in the stability and sensitivity of voltammetric and amperometric measurements of insulin compared to the individual (CNT or RuOx) coated electrodes. The enhanced electrocatalytic activity towards insulin is indicated from lowering the potential of the oxidation process (starting around 0.35 versus Ag/AgCl) and the substantially higher sensitivity over the entire potential range. A wide linear dynamic range (10-800 nM) was achieved with a detection limit of 1 nM. The marked electrocatalytic activity of the RuOx/CNT coating towards insulin is coupled with a greatly enhanced stability. For example, the insulin amperometric response of the RuOx/CNT-coated electrodes is highly stable, with 97% of the initial activity remaining after 60 min stirring of 2 × 10⁻⁶ M solution (compared to significantly faster current diminutions at the RuOx- or CNT-coated surfaces). The results suggest great promise for miniaturized sensors and detectors for monitoring insulin.     

A carbon nanotubes assisted strategy for insulin detection and insulin proteolysis assay

The carbon nanotubes (CNTs) assisted strategy has been proposed for insulin sensing and insulin proteolysis analysis. Experiments demonstrated that this strategy could be used for trace insulin determination with a low detection limit 7.75 ng mL⁻¹ (S/N = 3) and a detection range from 20 ng mL⁻¹ to 400 ng mL⁻¹. Both biocompatibility and intrinsic conductivity of pristine CNTs enabled them to act an excellent biosensing platform for the realization of direct electrochemistry and electrocatalysis of insulin. Compared with the present methods, the proposed strategy could realize the trace insulin detection without electrode modifications. It is more convenient and simpler than those based on the chemically modified electrodes. This method also made the CNTs as the indicator for insulin proteolysis analysis so that the biological process could be studied by electron microscope, electrochemical methods and digital camera. CNTs obtained after the proteolysis showed the same capabilities as the pristine ones in electrochemical signal enhancement and could participate in the bio-circle repeatedly.     

Electrochemical oxidation and determination of ceftriaxone on a glassy carbon and carbon-nanotube-modified glassy carbon electrodes

The electrochemical behavior of ceftriaxone was investigated on a carbon-nanotube-modified glassy carbon (GC-CNT) electrode in a phosphate buffer solution, pH = 7.40, and the results were compared with those obtained using the unmodified one [glassy carbon (GC) electrode]. During oxidation of ceftriaxone, an irreversible anodic peak appeared, using both modified and unmodified electrodes. Cyclic voltammetric studies indicated that the oxidation process is irreversible and diffusion-controlled. The number of electrons exchanged in the electrooxidation process was obtained, and the data indicated that ceftriaxone is oxidized via a one-electron step. The results revealed that carbon nanotube promotes the rate of oxidation by increasing the peak current. In addition, ceftriaxone was oxidized at lower potentials, which thermodynamically is more favorable. These results were confirmed by impedance measurements. The electron-transfer coefficients and heterogeneous electron-transfer rate constants for ceftriaxone were reported using both the GC and GC-CNT electrodes. Furthermore, the diffusion coefficient of ceftriaxone was found to be 2.74 × 10⁻⁶ cm² s⁻¹. Binding of ceftriaxone to human serum albumin forms a kind of electroreactive species. The percentage of interaction of ceftriaxone with protein was also addressed. A sensitive, simple, and time-saving differential-pulse voltammetric procedure was developed for the analysis of ceftriaxone, using the GC-CNT electrode. Ceftriaxone can be determined with a detection limit of 4.03 × 10⁻⁶ M with the proposed method.     

Development of liposomal immunosensor for the measurement of insulin with femtomole detection

The monitoring of insulin is of great relevance for the management of diabetes, the detection of pancreatic islet-cell malfunction, the definition of hypoglycemia, and the diagnosis of insulinoma. A liposomal immunosensing system for the determination of insulin was developed in this study. The insulin sensor was constructed by the immobilization of anti-insulin antibodies on the inner wall of the microcapillary immunoseparator. Liposomes tagged with anti-insulin and encapsulating a fluorescent dye were used as the detectable label. In the presence of insulin, sandwich immunocomplexes were formed between the immobilized antibodies in the column, the sample of insulin, and the antibody-tagged sulforhodamine B-dye-loaded liposomes. Signals generated by lysing the bound liposomes with 30 mM n-octyl-β-d-glucopyranoside were measured by a fluorescence detector. The detected signal was directly proportional to the amount of insulin in the test sample. The liposomal immunosensing system successfully detected as low as 136 attomole. MeOH (30%) was used for the regeneration of antibody-binding sites in the microcapillary after each measurement, which allowed the immunoseparator to be used for at least 70 repeated assays. The antibody activity in this proposed microcapillary immunoseparator could be well maintained for at least 1 week. The calibration curve for insulin in Tris-buffered saline had a linear dynamic range of 10 pM-10 nM, and the total assay time was less than 30 min. The coefficient of variation for triplicate measurements was <5.00%, which indicated that well-reproducible results can be obtained by this newly developed method.     

Electrochemical Sensors Based on Carbon Nanotubes

Carbon nanotubes are attractive new materials. It has been about a decade since carbon nanotubes were discovered. Carbon nanotubes have many outstanding properties and have many practical or potential applications. In this short review we introduce recent advances in carbon nanotubes as potential material for electrochemical sensors. The advantages of carbon nanotubes as sensors are discussed along with future prospects.     

Electrochemical detection of phenolic estrogenic compounds at carbon nanotube-modified electrodes

The use of a carbon nanotube-modified glassy carbon electrode (CNT-GCE) for the LC-EC detection of phenolic compounds with estrogenic activity is reported. Cyclic voltammograms for phenolic endocrine disruptors and estrogenic hormones showed, in general, an enhancement of their electrochemical oxidation responses at CNT-GCE attributable to the electrocatalytic effect caused by CNTs. Hydrodynamic voltammograms obtained under flow injection conditions lead to the selection of +700 mV as the potential value to be applied for the amperometric detection of the phenolic estrogenic compounds, this value being remarkably less positive than those reported in the literature using other electrode materials. Successive injections of these compounds demonstrated that no electrode surface fouling occurred. A mobile phase consisting of a 50:50 (v/v) acetonitrile:0.05 mol l⁻¹ phosphate buffer of pH 7.0 was selected for the chromatographic separation of mixtures of these compounds, with detection limits ranging between 98 and 340 nmol l⁻¹. Good recoveries were obtained in the analysis of underground well water and tap water samples spiked with some phenolic estrogenic compounds at a 14 nmol l⁻¹ concentration level.     

Electrochemical Behavior and Determination of Phenylephrine at Silicate Nanotubes Modified Electrode

A novel Silicate nanotubes (SNTs) modified glass carbon (GC) electrode was prepared and used to study the electrochemcial behavior of phenylephrine (PHE) and determine it. The enhanced electrochemical response of PHE at SNTs modified electrode was observed as compared with bare GC electrode. This proposed method displayed a broad linear range and a lower detection limit for PHE. The linear range was from 8 × 10^?8 M to 2 × 10^?5 M with the detection limit of 1 × 10^?8 M. The electrode could be easily regenerated and exhibited high stability and good selectivity. This method was successfully applied to the determination of PHE in drug samples with satisfactory result. The strategy presented here opens a new way for the development of nanoelectronic devices or electrochemical sensors based on SNTs.     

Electrochemical antitumor drug sensitivity test for leukemia K562 cells at a carbon-nanotube-modified electrode

The change in electrochemical behavior of tumor cells induced by antitumor drugs was detected by using a multiwall carbon nanotubes (MWNTs)-modified glass carbon electrode (GCE). Based on the changes observed, a simple, in vitro, electrochemical antitumor drug sensitivity test was developed. MWNTs promoted electron transfer between the electroactive centers of cells and the electrode. Leukemia K562 cells exhibited a well-defined anodic peak of guanine at +0.823 V at 50 mV s(-1). HPLC assay with ultraviolet detection was used to elucidate the reactant responsible for the electrochemical response of the tumor cells. The guanine content within the cytoplasm of each K562 cell was detected to be 920 amol. For the drug sensitivity tests, 5-fluorouracil (5-FU) and several clinical antitumor drugs, such as vincristine, adriamycin, and mitomycin C, were added to cell culture medium. As a result, the electrochemical responses of the K562 cells decreased significantly. The cytotoxicity curves and results obtained corresponded well with the results of MTT assays. In comparison to conventional methods, this electrochemical test is highly sensitive, accurate, inexpensive, and simple. The method proposed could be developed as a convenient means to study the sensitivity of tumor cells to antitumor drugs.     

Comparison of the Electrochemical Reactivity of Carbon Nanotubes Paste Electrodes with Different Types of Multiwalled Carbon Nanotubes

Carbon nanotubes (CNTs) are widely used in electrochemical studies. It is reported that CNTs with different source and dispersed in different agents [1] yield significant difference of electrochemical reactivity. Here we report on the electrochemical performance of CNTs paste electrodes (CNTPEs) prepared by multiwalled carbon nanotubes (MWNTs) with different diameters, lengths and functional groups. The resulting electrodes exhibit remarkable different electrochemical reactivity towards redox molecules such as NADH and K₃[Fe(CN)₆]. It is found that CNTPEs prepared by MWNTs with 20–30 nm diameter show highest catalysis to NADH oxidation, while CNTPEs prepared by MWNTs with carboxylate groups have best electron‐transfer rate (The peak‐peak separation (ΔE_p) is +0.108 V for MWNTs with carboxylate groups, +0.155 V for normal MWNTs, and +0.174 V for short MWNTs) but weak catalysis towards oxidation of NADH owing to the hydrophilicity of carboxylate groups. The electrochemical reactivity depends on the lengths of CNTs to some extent. The ‘long’ CNTs perform better in our study (The oxidation signals of NADH appear below +0.39 V for ‘long’ CNTs and above +0.46 V for the ‘short’ one totally). Readers may get some directions from this article while choose CNTs for electrochemical study.     

Detection of homocysteine at carbon nanotube paste electrodes

The use of a carbon-nanotube paste (CNTP) electrode provides an effective means for the determination of homocysteine. A decrease of ca. 120 mV in the overpotential for the oxidation of homocysteine compared to a traditional carbon paste electrode, is reported along with greatly enhanced signal-to-noise characteristics. The analytical parameters have been assessed with a linear range from 5 to 200 μM and a detection limit of 4.6 μM. Furthermore, the generic nature of this increased reactivity of the CNTP surface towards thiol moieties has been demonstrated with cysteine, glutathione and n-acetylcysteine, providing a greatly enhanced electrochemical response compared to the carbon paste electrode.     

碳纳米管纯化对Pt/CNTs催化甲醇电化学氧化活性的影响

探索了一种适用于Pt/CNTs催化剂的纯化方法.利用比表面积测定、X射线衍射(XRD)、透射电子显微镜(TEM)和电化学等手段进行了表征.研究结果表明,经该方法纯化的CNTs作为载体制备的阳极催化剂表现出明显优于相应的混酸氧化法纯化的CNTs为载体的催化剂催化性能.     

Determination of trace heavy metals in herbs by sequential injection analysis-anodic stripping voltammetry using screen-printed carbon nanotubes electrodes

A method for the simultaneous determination of Pb(II), Cd(II), and Zn(II) at low μg L⁻¹ concentration levels by sequential injection analysis-anodic stripping voltammetry (SIA-ASV) using screen-printed carbon nanotubes electrodes (SPCNTE) was developed. A bismuth film was prepared by in situ plating of bismuth on the screen-printed carbon nanotubes electrode. Operational parameters such as ratio of carbon nanotubes to carbon ink, bismuth concentration, deposition time and flow rate during preconcentration step were optimized. Under the optimal conditions, the linear ranges were found to be 2-100 μg L⁻¹ for Pb(II) and Cd(II), and 12-100 μg L⁻¹ for Zn(II). The limits of detection (S_bl/S = 3) were 0.2 μg L⁻¹ for Pb(II), 0.8 μg L⁻¹ for Cd(II) and 11 μg L⁻¹ for Zn(II). The measurement frequency was found to be 10-15 stripping cycle h⁻¹. The present method offers high sensitivity and high throughput for on-line monitoring of trace heavy metals. The practical utility of our method was also demonstrated with the determination of Pb(II), Cd(II), and Zn(II) by spiking procedure in herb samples. Our methodology produced results that were correlated with ICP-AES data. Therefore, we propose a method that can be used for the automatic and sensitive evaluation of heavy metals contaminated in herb items.     

Electrochemical determination of sulphide at multi-walled carbon nanotubes-dihexadecyl hydrogen phosphate composite film modified electrodes based on in situ synthesis of methylene blue

A novel electrochemical method for the determination of sulphide at a multi-walled carbon nanotube-dihexadecyl hydrogen phosphate composite film coated glassy carbon electrode （MWNTs-DHP/GCE） based on in situ synthesis of methylene blue （MB） was established. 2007 Sheng Shui Hu. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.     

Amperometric determination of bovine insulin based on synergic action of carbon nanotubes and cobalt hexacyanoferrate nanoparticles stabilized by EDTA

A simple approach is proposed for the synthesis of cobalt hexacyanoferrate nanoparticles (CoNPs) with uniform shape and size controlled by ethylene diamine tetraacetic acid (EDTA) as a stabilizer. A sensitive amperometric biosensor for insulin has been prepared using glassy carbon electrodes by solubilization of carbon nanotubes (CNTs) in chitosan (CHIT) together with CoNPs synthesized by the new methodology. The CoNP-CNT-CHIT organic–inorganic system exerts a synergistic effect, resulting in the remarkably enhanced insulin currents owing to the superior electron-transfer ability of CNTs and the excellent reversible redox centers of CoNPs. High-resolution transmission electron microscopy (HRTEM) was used to provide closer inspection of the CoNPs. The effects of alkali metal cations and the concentrations of CNTs and CoNPs on the voltammetric behavior of the film-modified electrode were also investigated. In pH 6.98 phosphate buffer (PB) at +0.7 V (vs. SCE) the insulin biosensor exhibits a linear response range of 0.1–3 μM with a correlation coefficient of 0.98, and the detection limit (S/N=3) is determined to be 40 nM, the stability of the biosensor was tested and found satisfactory. There is great promise for in vivo measurements of this important hormone.     

Electrochemical reduction and voltammetric determination of metronidazole at a nanomaterial thin film coated glassy carbon electrode

Simple and sensitive electrochemical method for the determination of metronidazole, based on a nanostructured film coated glassy carbon electrode (GCE), is described. Multi-walled carbon nanotubes (MWNT) was dispersed into water in the presence of a hydrophobic surfactant to give very stable and homogeneous MWNT suspension, and a MWNT-film coated GCE was achieved via evaporating solvent. Metronidazole yields a well-defined reduction peak whose potential is −0.71 V at the MWNT-film coated GCE in pH 9.0 Britton-Robinson buffer. Compared with bare GCE, the MWNT-film modified GCE significantly enhances the reduction peak current of metronidazole. All the experimental parameters were optimized for the determination of metronidazole. The detection limit is 6×10⁻⁹ mol/l at 2 min accumulation. This method has been successfully used to determine metronidazole in the drugs. Furthermore, results obtained by the proposed method have been compared with spectrophotometric method.     

Electrocatalytic detection of phenolic estrogenic compounds at NiTPPS|carbon nanotube composite electrodes

A Ni(II)tetrakis(4-sulfonatophenyl) porphyrin (NiTPPS)|carbon nanotube composite electrode that shows strong catalytic and antifouling capability was developed to detect a series of phenolic endocrine compounds including bisphenol A, nonylphenol and ethynylestradiol. This electrode was fabricated by electropolymerizing NiTPPS complexes on a carbon nanotube-modified glassy carbon electrode. Optimized experimental parameters including a hydrodynamic potential of 0.7 V for flow injection analysis (FIA) and a NiTPPS surface coverage of 2.2 nmol cm⁻² (standard deviation 0.2 nmol cm⁻²; n = 6) were obtained for detection of the endocrine disrupting compounds. The sensor responded well to all the tested compounds with limits of detection ranging from 15 nmol L⁻¹ to 260 nmol L⁻¹ (based on three times S/N ratio) under FIA conditions. Both carbon nanotubes and NiTPPS account for the excellent performance of the composite modified electrode.     

Nicotinamide Adenine Dinucleotide Oxidation Studies at Multiwalled Carbon Nanotube/Polymer Composite Modified Glassy Carbon Electrodes

NADH oxidation has previously been investigated at carbon nanotube surfaces, although studies into the effect of the polymer binders are needed to fully understand whether the polymer binder affects the electrochemistry. This work details NADH oxidation at glassy carbon electrodes modified with composites containing multiwalled carbon nanotubes and selected polymer binders. NADH is shown to be oxidized at a lower potential than at glassy carbon electrodes and the oxidation potential is a function of the polymer binder. Hydrophobically modified Nafion, Nafion, linear poly(ethylenimine) (LPEI), octyl‐modified LPEI, and poly(vinylpyridine) binders were studied. Experiments showed the peak current and electrochemically assessible electrode area are dependent on the polymer binder. Overall, this paper shows that polymer binders affect NADH oxidation potential at carbon nanotube modified electrodes.     

Preparation and Characterization of Electrodes Modified with Pyrrole Surfactant,Multiwalled Carbon Nanotubes and Metallophthalocyanines for the Electrochemical Detection of Thiols

Our aim was to prepare hybrid electrodes active towards the electrooxidation of thiols by the co‐immobilization of native carbon nanotubes (CNTs) and cobalt phthalocyanine (CoPc) from aqueous solutions. This strategy was adopted to avoid the oxidation of CNTs that can induce a modification of their exceptional properties. To do so, a hydrosoluble pyrrole surfactant was used to get homogeneous aqueous dispersions of CNTs and CoPc and to trap both materials on the electrode via the electropolymerization of the pyrrole surfactant. The hybrid electrodes exhibit a good electrocatalytic activity towards the oxidation of L ‐cysteine and glutathione. Their performances in terms of limit of detection (0.01 mM) are compatible with the detection of these thiols in biological samples.     

Electrocatalytic Dioxygen Reduction at Glassy Carbon Electrode Modified with Polyaniline Grafted Multiwall Carbon Nanotube Film

The work details the electrocatalysis of oxygen reduction reaction (ORR) in 0.5 M H₂SO₄ medium on a modified electrode containing a film of polyaniline (PANI) grafted multi‐wall carbon nanotube (MWNT) over the surface of glassy carbon electrode. We have fabricated a novel modified electrode in which conducting polymer is present as connected unit to MWNT. The GC/PANI‐g‐MWNT modified electrode (ME) is fabricated by electrochemical polymerization of a mixture of amine functionalized MWNT and aniline with GC as working electrode. Cyclic voltammetry and amperometry are used to demonstrate the electrocatalytic activity of the GC/PANI‐g‐MWNT‐ME. The GC/PANI‐g‐MWNT‐ME exhibits remarkable electrocatalytic activity for ORR. A more positive onset potential and higher catalytic current for ORR are striking features of GC/PANI‐g‐MWNT‐ME. Rapid and high sensitivity of GC/PANI‐g‐MWNT‐ME to ORR are evident from the higher rate constant (7.92×10² M^?1 s^?1) value for the reduction process. Double potential chronoamperometry and rotating disk and rotating ring‐disk electrode (RRDE) experiments are employed to investigate the kinetic parameters of ORR at this electrode. Results from RDE and RRDE voltammetry demonstrate the involvement of two electron transfer in oxygen reduction to form hydrogen peroxide in acidic media.