Immunosensor based on carbon nanotube/manganese dioxide electrochemical tags

This article reports on carbon nanotube/manganese dioxide (CNT–MnO₂) composites as electrochemical tags for non-enzymatic signal amplification in immunosensing. The synthesized CNT–MnO₂ composites showed good electrochemical activity, electrical conductivity and stability. The electrochemical signal of CNT–MnO₂ composites coated glassy carbon electrode (GCE) increased by nearly two orders of magnitude compared to bare GCE in hydrogen peroxide (H₂O₂) environment. CNT–MnO₂ composite was subsequently validated as electrochemical tags for sensitive detection of α-fetoprotein (AFP), a tumor marker for diagnosing hepatocellular carcinoma. The electrochemical immunosensor demonstrated a linear response on a log-scale for AFP concentrations ranging from 0.2 to 100 ng mL⁻¹. The limit of detection (LOD) was estimated to be 40 pg mL⁻¹ (S/N = 3) in PBS buffer. Further measurements using AFP spiked plasma samples revealed the applicability of fabricated CNT–MnO₂ composites for clinical and diagnostic applications.     

Graphene–palladium nanowires based electrochemical sensor using ZnFe2O4–graphene quantum dots as an effective peroxidase mimic

We proposed an electrochemical DNA sensor by using peroxidase-like magnetic ZnFe₂O₄–graphene quantum dots (ZnFe₂O₄/GQDs) nanohybrid as a mimic enzymatic label. Aminated graphene and Pd nanowires were successively modified on glassy carbon electrode, which improved the electronic transfer rate as well as increased the amount of immobilized capture ssDNA (S1). The nanohybrid ZnFe₂O₄/GQDs was prepared by assembling the GQDs on the surface of ZnFe₂O₄ through a photo-Fenton reaction, which was not only used as a mimic enzyme but also as a carrier to label complementary ssDNA (S3). By synergistically integrating highly catalytically activity of nano-sized GQDs and ZnFe₂O₄, the nanohybrid possessed highly-efficient peroxidase-like catalytic activity which could produce a large current toward the reduction of H₂O₂ for signal amplification. Thionine was used as an excellent electron mediator. Compared with traditional enzyme labels, the mimic enzyme ZnFe₂O₄/GQDs exhibited many advantages such as environment friendly and better stability. Under the optimal conditions, the approach provided a wide linear range from 10⁻¹⁶ to 5 × 10⁻⁹ M and low detection limit of 6.2 × 10⁻¹⁷ M. The remarkable high catalytic capability could allow the nanohybrid to replace conventional peroxidase-based assay systems. The new, robust and convenient assay systems can be widely utilized for the identification of other target molecules.     

A highly sensitive hydrogen peroxide amperometric sensor based on MnO2-modified vertically aligned multiwalled carbon nanotubes

In this report, a highly sensitive amperometric sensor based on MnO₂-modified vertically aligned multiwalled carbon nanotubes (MnO₂/VACNTs) for determination of hydrogen peroxide (H₂O₂) was fabricated by electrodeposition. The morphology of the nanocomposite was characterized by scanning electron microscopy, energy-dispersive X-ray spectrometer and X-ray diffraction. Cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy were applied to investigate the electrochemical properties of the MnO₂/VACNTs nanocomposite electrode. The mechanism for the electrochemical reaction of H₂O₂ at the MnO₂/VACNTs nanocomposite electrode was also discussed. In borate buffer (pH 7.8, 0.20 M), the MnO₂/VACNTs nanocomposite electrode exhibits a linear dependence (R = 0.998) on the concentration of H₂O₂ from 1.2 × 10⁻⁶ M to 1.8 × 10⁻³ M, a high sensitivity of 1.08 × 10⁶ μA M⁻¹ cm⁻² and a detection limit of 8.0 × 10⁻⁷ M (signal/noise = 3). Meanwhile, the MnO₂/VACNTs nanocomposite electrode is also highly resistant towards typical inorganic salts and some biomolecules such as acetic acid, citric acid, uric acid and d-(+)-glucose, etc. In addition, the sensor based on the MnO₂/VACNTs nanocomposite electrode was applied for the determination of trace of H₂O₂ in milk with high accuracy, demonstrating its potential for practical application.     

Electrochemically Prepared Three‐dimensional Porous Nitrogen‐doped Graphene Modified Electrode for Non‐enzymatic Detection of Hydrogen Peroxide

A facile and green electrochemical method for the fabrication of three‐dimensional porous nitrogen‐doped graphene (3DNG) modified electrode was reported. This method embraces two consecutive steps: First, 3D graphene/polypyrrole (ERGO/PPy) composite was prepared by electrochemical co‐deposition of graphene and polypyrrole on a gold foil. Subsequently, the ERGO/PPy composite modified gold electrode was annealed at high temperature. Thus 3DNG modified electrode was obtained. Scanning electron microscopy (SEM), X‐ray photoelectron spectroscopy (XPS) and Raman spectroscopy were used to characterize the structure and morphology of the electrode. The electrode exhibits excellent electroanalytical performance for the reduction of hydrogen peroxide (H₂O₂). By linear sweep voltammetric measurement, the cathodic peak current was linearly proportional to H₂O₂ concentration in the range from 0.6 μM to 2.1 mM with a sensitivity of 1.0 μA μM⁻¹ cm⁻². The detection limit was ascertained to be 0.3 μM. The anti‐interference ability, reproducibility and stability of the electrode were carried out and the electrode was applied to the detection of H₂O₂ in serum sample with recoveries from 98.4 % to 103.2 %.     

Simultaneous determination of uric acid,xanthine, hypoxanthine and caffeine in human blood serum and urine samples using electrochemically reduced graphene oxide modified electrode

This paper describes the fabrication of graphene on glassy carbon electrode (GCE) by electrochemical reduction of graphene oxide (GO) attached through 1,6-hexadiamine on GCE and the simultaneous determination of structurally similar four purine derivatives using the resultant electrochemically reduced GO (ERGO) modified electrode. The electrocatalytic activity of ERGO was investigated toward the oxidation of four important purine derivatives, uric acid (UA), xanthine (XN), hypoxanthine (HXN) and caffeine (CAF) at physiological pH. The modified electrode not only enhanced the oxidation currents of the four purine derivatives but also shifted their oxidation potentials toward less positive potentials in contrast to bare GCE. Further, it successfully separates the voltammetric signals of the four purine derivatives in a mixture and hence used for the simultaneous determination of them. Selective determination of one purine derivative in the presence of low concentrations other three purine derivatives was also realized at the present modified electrode. Using differential pulse voltammetry, detection limits of 8.8 × 10⁻⁸ M, 1.1 × 10⁻⁷ M, 3.2 × 10⁻⁷ M and 4.3 × 10⁻⁷ M were obtained for UA, XN, HXN and CAF, respectively. The practical application of the modified electrode was demonstrated by simultaneously determining the concentrations of UA, XN, HXN and CAF in human blood plasma and urine samples.     

A highly sensitive electrochemical sensor for simultaneous determination of hydroquinone and bisphenol A based on the ultrafine Pd nanoparticle@TiO2 functionalized SiC

A titanium dioxide–silicon carbide nanohybrid (TiO₂–SiC) with enhanced electrochemical performance was successfully prepared through a facile generic in situ growth strategy. Monodispersed ultrafine palladium nanoparticles (Pd NPs) with a uniform size of ∼2.3 nm were successfully obtained on the TiO₂–SiC surface via a chemical reduction method. The Pd-loaded TiO₂–SiC nanohybrid (Pd@TiO₂–SiC) was characterized by transmission electron microscopy and X-ray diffractometry. A method for the simultaneous electrochemical determination of hydroquinone (HQ) and bisphenol A (BPA) using a Pd@TiO₂–SiC nanocomposite-modified glassy carbon electrode was established. Utilizing the favorable properties of Pd NPs, the Pd@TiO₂–SiC nanohybrid-modified glassy carbon electrode exhibited electrochemical performance superior to those of TiO₂–SiC and SiC. Differential pulse voltammetry was successfully used to simultaneously quantify HQ and BPA within the concentration range of 0.01–200 μM under optimal conditions. The detection limits (S/N = 3) of the Pd@TiO₂–SiC nanohybrid electrode for HQ and BPA were 5.5 and 4.3 nM, respectively. The selectivity of the electrochemical sensor was improved by introducing 10% ethanol to the buffer medium. The practical application of the modified electrode was demonstrated by the simultaneous detection of HQ and BPA in tap water and wastewater samples. The simple and straightforward strategy presented in this paper are important for the facile fabrication of ultrafine metal NPs@metal oxide–SiC hybrids with high electrochemical performance and catalytic activity.     

Highly accessible Pt nanodots homogeneously decorated on Au nanorods surface for sensing

Some nanostructures are reported to possess enzyme-mimetic activities similar to those of natural enzymes. Herein, highly-dispersed Pt nanodots on Au nanorods (HD- PtNDs@AuNRs) with mimetic peroxidase activity were designed as an active electrode modifier for fabrication of a hydrogen peroxide (H₂O₂) electrochemical sensor. The HD-PtNDs@AuNRs were synthesized by a seed-mediated growth approach and confirmed by scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, and UV–vis spectroscopy. The electrochemical and catalytical performances of HD-PtNDs@AuNRs towards H₂O₂ reduction were investigated in detail by cyclic voltammetry and amperometry. The HD-PtNDs@AuNRs modified electrode displayed a high catalytic activity to H₂O₂ at −0.10 V (versus SCE), a rapid response within 5 s, a wide linear range of 2.0–3800.0 μM, a detection limit of 1.2 μM (S/N = 3), and a high sensitivity of 181 μA mM⁻¹ cm⁻². These results suggested a promising potential of fabricating H₂O₂ electrochemical sensor using HD- PtNDs@AuNRs.     

Enhancing selectivity in spectrofluorimetric determination of tryptophan by using graphene oxide nanosheets

Reaction of formaldehyde with amino acids followed by oxidation with hydrogen peroxide to produce a fluorophore Norharman product is well known and was used for the spectrofluorimetric determination of l-tryptophan (Trp). This study aimed to use graphene oxide (GO) to enhance the selectivity and sensitivity of Trp in presence of other amino acids and possible interfering compounds. Different parameters such as pH, temperature, incubation time, and concentrations of formaldehyde, H₂O₂ and GO were studied to optimize the condition of determination. Experimental data showed that the maximum fluorescence intensity was achieved in pH 7.0–9.0 phosphate buffer mixed with 7–10% (v/v) formaldehyde and 1–2% (v/v) H₂O₂ as oxidizing agent at 60 ?C for 1 h. On the basis of calibration curve of various concentrations of Trp in the presence of 20 μg mL⁻¹ GO, the lower limit of detection (LOD) of Trp was determined as 0.092 nmol mL⁻¹ and the lower limit of quantification (LOQ) was 0.3 nmol mL⁻¹. The selectivity of Trp in presence of other amino acids and possible interfering compounds were studied with and without GO. The data obtained after inner filter effect corrections revealed that the selectivity of Trp in presence of amino acids and other possible interfering agents was improved in the range of 76–96%, compared with that in absence of GO. The enhancement of selectivity in the presence of GO indicates that the Trp and other amino acid and possible interfering compounds were adsorbed by GO, and the selective uptaking of Trp-by the reaction with formaldehyde followed by oxidation with H₂O₂ at 60 ?C with high selectivity and sensitivity was achieved successfully.     

Highly sensitive luminol electrochemiluminescence immunosensor based on ZnO nanoparticles and glucose oxidase decorated graphene for cancer biomarker detection

In this work, we reported a sandwiched luminol electrochemiluminescence (ECL) immunosensor using ZnO nanoparticles (ZnONPs) and glucose oxidase (GOD) decorated graphene as labels and in situ generated hydrogen peroxide as coreactant. In order to construct the base of the immunosensor, a hybrid architecture of Au nanoparticles and graphene by reduction of HAuCl₄ and graphene oxide (GO) with ascorbic acid was prepared. The resulted hybrid architecture modified electrode provided an excellent platform for immobilization of antibody with good bioactivity and stability. Then, ZnONPs and GOD functionalized graphene labeled secondary antibody was designed for fabricating a novel sandwiched ECL immunosensor. Enhanced sensitivity was obtained by in situ generating hydrogen peroxide with glucose oxidase and the catalysis of ZnONPs to the ECL reaction of luminol–H₂O₂ system. The as-prepared ECL immunosensor exhibited excellent analytical property for the detection of carcinoembryonic antigen (CEA) in the range from 10 pg mL⁻¹ to 80 ng mL⁻¹ and with a detection limit of 3.3 pg mL⁻¹ (S N⁻¹ = 3). The amplification strategy performed good promise for clinical application of screening of cancer biomarkers.     

Electrochemical Fabrication of Prussian Blue Nanocube‐decorated Electroreduced Graphene Oxide for Amperometric Sensing of NADH

In this study, Prussian blue (PB) film on the electroreduced graphene oxide (ERGO)‐modified Au electrode surface (ERGO/PB) is easily prepared by means of cyclic voltammetric technique in the mixture of K₃Fe(CN)₆ and FeCl₃. Its electrochemical behaviors for NADH biosensor are studied. The structural and morphological characters of modified electrode material are analyzed with using of XPS, XRD, Raman, EDS, and SEM techniques. ERGO/PB hybrid nanocomposite for NADH biosensor is exhibited to the higher catalytic effect (linear range from 1.0 to 100 μM, detection limit of 0.23 μM at S/N=3) compared to naked Au, ERGO‐modified Au, and PB‐modified Au electrodes. In addition to, ERGO/PB electrode was used to voltammetric and amperometric detection of H₂O₂. ERGO/PB electrodes also showed the same behavior as the NADH sensor. This ERGO/PB‐modified electrode supplied a simple, new, and low‐cost route for amperometric sensing of both NADH and H₂O₂.