Doble role of bathocuproine disulfonic acid as multi-walled carbon nanotubes dispersing agent and copper preconcentration ligand: Analytical applications for the development of hydrogen peroxide and glucose electrochemical sensors.

We are reporting a new strategy for preparing carbon nanotubes (CNTs)-based hydrogen peroxide and glucose amperometric sensors by taking advantage of the dual role of bathocuproine disulfonic acid (BCS) as dispersing agent of multi-walled carbon nanotubes (MWCNTs) and as ligand for the preconcentration of Cu(II). The platform was obtained by casting glassy carbon electrodes (GCE) with the dispersion of MWCNTs in BCS (MWCNTs-BCS) followed by the preconcentration of Cu(II) by surface complex formation at open circuit potential (GCE/MWCNTs-BCS/Cu). The resulting electrode was used for the sensitive amperometric quantification of hydrogen peroxide at 0.400 V catalyzed by the preconcentrated copper, with a linear range between 5.0 × 10-7 and 7.4 × 10-6 M, a sensitivity of 24.3 mA.M-1, and a detection limit of 0.2 µM. The adsorption of GOx at GCE/MWCNTs-BCS/Cu followed by the immobilization of Nafion (Naf), allowed the construction of a sensitive and selective amperometric glucose biosensor with a linear range between 5.0 × 10-6 M and 4.9 × 10-4 M, a sensitivity of (477 ± 3) µA.M-1 and a detection limit of 2 µM. The proposed (bio)sensors were successfully used for the quantification of hydrogen peroxide in enriched milk samples and glucose in milk and commercial beverages without any pretreatment.

Multi-walled carbon nanotubes functionalized with bathocuproinedisulfonic acid: analytical applications for the quantification of Cu(II).

This work reports the successful non-covalent functionalization of multi-walled carbon nanotubes (MWCNTs) with bathocuproinedisulfonic acid (BCS) and the analytical application of the resulting dispersion (MWCNTs-BCS) to develop an electrochemical sensor for Cu(II) quantification. The sensor was obtained by casting glassy carbon electrodes (GCEs) with MWCNTs-BCS. The sensing mechanism was based on the open circuit preconcentration of Cu(II) at the electrode surface by complexation of Cu(II) through the phenanthroline ring nitrogen of the BCS that supports the MWCNTs, the reduction of the preconcentrated Cu(II), and final differential pulse voltammetry-anodic stripping in 0.020 M acetate buffer, pH 5.00. The sensitivity of the sensor was (2.73 ± 0.08) µA µM-1, with a linear range between 5.0 × 10-7 M and 6.0 × 10-6 M, a detection limit of 0.15 µM (9.5 µg L-1), and reproducibility of 6.2% using the same dispersion and 7.1% using three different MWCNTs-BCS dispersions. The quantification of Cu(II) was highly selective even in the presence of As3+, Cr3+, Cd2+, Ni2+, Pb2+, Co2+, Zn2+, Fe2+, Hg2+, Rh, Ir, and Ru. The proposed sensor was successfully used for quantifying Cu(II) in tap water. Graphical abstract.

Designing electrochemical interfaces based on nanohybrids of avidin functionalized-carbon nanotubes and ruthenium nanoparticles as peroxidase-like nanozyme with supramolecular recognition properties for site-specific anchoring of biotinylated residues.

We are reporting an original supramolecular architecture based on a rationally designed new nanohybrid with enhanced peroxidase-like activity and site-specific biorecognition properties using avidin-functionalized multi-walled carbon nanotubes (MWCNTs-Av) and Ru nanoparticles (RuNPs). The nanohybrid-electrochemical interface was obtained by drop-coating of MWCNTs-Av dispersion at glassy carbon electrodes (GCE) followed by solvent evaporation and further electrodeposition of RuNPs (50 ppm RuCl2 for 15 s at -0.600 V). The simultaneous presence of MWCNTs and RuNPs produces a synergic effect on the non-enzymatic catatalytic reduction of H2O2 and allows the quantification of H2O2 in a wide linear range (from 5.0 × 10-7 M to 1.75 × 10-3 M) with a low limit of detection (65 nM). The avidin residues present in MWCNTs-Av/RuNPs hybrid nanomaterial allowed the anchoring by bioaffinity of biotinylated glucose oxidase (biot-GOx) as proof-of-concept of the analytical application of MWCNTs-Av platform for biosensors development. The resulting nanoarchitecture behaves as a bienzymatic-like glucose biosensor with a competitive analytical performance: linear range between 2.0 × 10-5 M and 1.23 × 10-3 M, sensitivity of (0.343 ±â€¯0.002) µA mM-1 or (2.60 ±â€¯0.02) µA mM-1 cm-2, detection limit of 3.3 µM, and reproducibility of 5.2% obtained with five different GCE/MWCNTs-Av/RuNPs/biot-GOx bioplatforms prepared the same day using the same MWCNTs-Av dispersion, and 9.1% obtained with nine biosensors prepared in different days with nine different MWCNTs-Av dispersions. The average concentrations of glucose in Gatorade®, Red bull® and Pepsi® with the biosensor demonstrated excellent agreement with those reported in the commercial beverages.

Co2TiO4/Reduced Graphene Oxide Nanohybrids for Electrochemical Sensing Applications.

For the first time, the synthesis, characterization, and analytical application for hydrogen peroxide quantification of the hybrid materials of Co2TiO4 (CTO) and reduced graphene oxide (RGO) is reported, using in situ (CTO/RGO) and ex situ (CTO+RGO) preparations. This synthesis for obtaining nanostructured CTO is based on a one-step hydrothermal synthesis, with new precursors and low temperatures. The morphology, structure, and composition of the synthesized materials were examined using scanning electron microscopy, X-ray diffraction (XRD), neutron powder diffraction (NPD), and X-ray photoelectron spectroscopy (XPS). Rietveld refinements using neutron diffraction data were conducted to determine the cation distributions in CTO. Hybrid materials were also characterized by Brunauer-Emmett-Teller adsorption isotherms, Scanning Electron microscopy, and scanning electrochemical microscopy. From an analytical point of view, we evaluated the electrochemical reduction of hydrogen peroxide on glassy carbon electrodes modified with hybrid materials. The analytical detection of hydrogen peroxide using CTO/RGO showed 11 and 5 times greater sensitivity in the detection of hydrogen peroxide compared with that of pristine CTO and RGO, respectively, and a two-fold increase compared with that of the RGO+CTO modified electrode. These results demonstrate that there is a synergistic effect between CTO and RGO that is more significant when the hybrid is synthetized through in situ methodology.

Amperometric aptasensor for carcinoembryonic antigen based on the use of bifunctionalized Janus nanoparticles as biorecognition-signaling element.

We report herein the design of a novel biosensing strategy for the detection of carcinoembryonic antigen (CEA), based on the use of Janus-type nanoparticles having Au and silica opposite faces as integrated electrochemical biorecognition-signaling system. The Janus nanoparticles were properly functionalized with horseradish peroxidase on the silica surface to act as signaling element, and a biotin thiol-modified anti-CEA DNA hairpin aptamer the Au face to assemble the biorecognition element. The sensing approach relies on the first specific recognition of CEA by the bifunctionalized Janus nanoparticles, causing unfolding of the DNA hairpin structure and unmasking the biotin residues at the aptamer chain. This CEA-Janus nanoparticle complex was then captured by avidin-modified Fe3O4@SiO2 NanoCaptors®, allowing further magnetic deposition on carbon screen printed electrodes for the amperometric detection of the cancer biomarker. The Janus nanoparticles-based aptasensor was able to detect CEA in the range from 1 to 5000 ng mL-1 (5.5 pM-28 nM) with a detection limit of 210 pg mL-1 (1.2 pM). The aptasensor also showed high reproducibility and storage stability, and was successfully validated in human serum.

Electrochemical biointerfaces based on carbon nanotubes-mesoporous silica hybrid material: Bioelectrocatalysis of hemoglobin and biosensing applications.

We are reporting a novel biosensing platform based on a hybrid nanomaterial that combines the advantages of Nafion-coated multiwalled carbon nanotubes (MWCNTs) and mesoporous silica MCM41 nanoparticles functionalized with hemoglobin (Hb). MWCNTs-MCM41-Hb hybrid bioconjugate was characterized by scanning electron microscopy (SEM), UV-vis spectroscopy and electrochemical techniques after deposition at glassy carbon electrodes (GCE). The combination of the high surface area, biocompatibility and protein loading capacity of MCM41 nanoparticles and the high surface area and catalytic properties of MWCNTs allowed the direct electron transfer (DET) between Hb and the electrode surface. The electron transfer rate constant (k) and the surface coverage of electroactive Hb (ΓHb) were 5.2 s-1 and 4.7 × 10-10 mol cm-2, respectively. The GCE modified with the nanostructured architecture (GCE/MWCNTs-MCM41-Hb) was successfully used as a third-generation biosensor for the highly sensitive and selective quantification of nitrite (NO2-) and trichloroacetic acid (TCA) by taking advantage of the excellent biocatalytic activity of Hb and the efficient direct charge transfer of the heme group.

Single-walled carbon nanotubes covalently functionalized with polytyrosine: A new material for the development of NADH-based biosensors.

We report for the first time the use of single-walled carbon nanotubes (SWCNT) covalently functionalized with polytyrosine (Polytyr) (SWCNT-Polytyr) as a new electrode material for the development of nicotinamide adenine dinucleotide (NADH)-based biosensors. The oxidation of glassy carbon electrodes (GCE) modified with SWCNT-Polytyr at potentials high enough to oxidize the tyrosine residues have allowed the electrooxidation of NADH at low potentials due to the catalytic activity of the quinones generated from the primary oxidation of tyrosine without any additional redox mediator. The amperometric detection of NADH at 0.200V showed a sensitivity of (217±3)µAmM(-1)cm(-2) and a detection limit of 7.9nM. The excellent electrocatalytic activity of SWCNT-Polytyr towards NADH oxidation has also made possible the development of a sensitive ethanol biosensor through the immobilization of alcohol dehydrogenase (ADH) via Nafion entrapment, with excellent analytical characteristics (sensitivity of (5.8±0.1)µAmM(-1)cm(-2), detection limit of 0.67µM) and very successful application for the quantification of ethanol in different commercial beverages.

Covalent functionalization of single-walled carbon nanotubes with polytyrosine: Characterization and analytical applications for the sensitive quantification of polyphenols.

This work reports the synthesis and characterization of single-walled carbon nanotubes (SWCNT) covalently functionalized with polytyrosine (Polytyr); the critical analysis of the experimental conditions to obtain the efficient dispersion of the modified carbon nanotubes; and the analytical performance of glassy carbon electrodes (GCE) modified with the dispersion (GCE/SWCNT-Polytyr) for the highly sensitive quantification of polyphenols. Under the optimal conditions, the calibration plot for the amperometric response of gallic acid (GA) shows a linear range between 5.0 × 10(-7) and 1.7 × 10(-4) M, with a sensitivity of (518 ± 5) m AM(-1) cm(-2), and a detection limit of 8.8 nM. The proposed sensor was successfully used for the determination of total polyphenolic content in tea extracts.

Seed-mediated growth of jack-shaped gold nanoparticles from cyclodextrin-coated gold nanospheres.

Branched gold nanoparticles were prepared by a seed-mediated approach using per-6-thio-6-deoxy-ß-cyclodextrin capped gold nanospheres as seeds and a growth medium similar to those commonly employed to prepare gold nanorods, containing AgNO3, ascorbic acid and cetyltrimethylammonium bromide. Novel jack-shaped gold nanoparticles (102-105 nm) were obtained at a specific range of Ag(+) ion concentrations (62-102 µM). The crystalline structure of these nanoparticles was confirmed by high-resolution transmission electron microscopy. The influence of the perthiolated ß-cyclodextrin on the successful preparation of gold nanojacks was demonstrated. The jack-shaped gold nanoparticles showed strong absorption in the near infrared region and excellent catalytic activity for the electrochemical oxidation of H2O2.

Supramolecular immobilization of xanthine oxidase on electropolymerized matrix of functionalized hybrid gold nanoparticles/single-walled carbon nanotubes for the preparation of electrochemical biosensors.

Glassy carbon electrodes modified with single-walled carbon nanotubes and a three-dimensional network of electropolymerized Au nanoparticles capped with 2-mercaptoethanesulfonic acid, p-aminothiophenol, and 1-adamantanethiol were used as hybrid electrochemical platforms for supramolecular immobilization of a synthesized artificial neoglycoenzyme of xanthine oxidase and ß-cyclodextrin through host-guest interactions. The ensemble was further employed for the bioelectrochemical determination of xanthine. The biosensor showed fast amperometric response within 5 s and a linear behavior in the 50 nM to 9.5 µM xanthine concentration range with high sensitivity, 2.47 A/(M cm(2)), and very low detection limit of 40 nM. The stability of the biosensor was significantly improved and the interferences caused by ascorbic and uric acids were noticeably minimized by coating the electrode surface with a Nafion thin film.

Electropolymerized network of polyamidoamine dendron-coated gold nanoparticles as novel nanostructured electrode surface for biosensor construction.

Polyfuntionalized gold nanoparticles were prepared by using 2-mercaptoethanesulfonic acid, p-aminothiophenol and cysteamine core polyamidoamine G-4 dendron as capping ligands. The nanoparticles were electropolymerized on a Au electrode surface through the formation of a bisaniline-cross-linked network. The enzyme tyrosinase was further crosslinked on this nanostructured matrix. The enzyme electrode, poised at -100 mV, was used for the amperometric quantification of cathecol. The biosensor showed a linear response from 50 nM to 10 µM cathecol, with a low detection limit of 20 nM and a sensitivity of 1.94 A M(-1) cm(2). The electrode retained 96% and 67% of its initial activity after 16 and 30 days of storage at 4 °C under dry conditions.

Designing electrochemical interfaces with functionalized magnetic nanoparticles and wrapped carbon nanotubes as platforms for the construction of high-performance bienzyme biosensors.

The design of a novel biosensing electrode surface, combining the advantages of magnetic ferrite nanoparticles (MNPs) functionalized with glutaraldehyde (GA) and poly(diallyldimethylammonium chloride) (PDDA)-coated multiwalled carbon nanotubes (MWCNTs) as platforms for the construction of high-performance multienzyme biosensors, is reported in this work. Before the immobilization of enzymes, GA-MNP/PDDA/MWCNT composites were prepared by wrapping of carboxylated MWCNTs with positively charged PDDA and interaction with GA-functionalized MNPs. The nanoconjugates were characterized by scanning electron microscopy (SEM) and electrochemistry. The electrode platform was used to construct a bienzyme biosensor for the determination of cholesterol, which implied coimmobilization of cholesterol oxidase (ChOx) and peroxidase (HRP) and the use of hydroquinone as redox mediator. Optimization of all variables involved in the preparation and analytical performance of the bienzyme electrode was accomplished. At an applied potential of -0.05 V, a linear calibration graph for cholesterol was obtained in the 0.01-0.95 mM concentration range. The detection limit (0.85 µM), the apparent Michaelis-Menten constant (1.57 mM), the stability of the biosensor, and the calculated activation energy can be advantageously compared with the analytical characteristics of other CNT-based cholesterol biosensors reported in the literature. Analysis of human serum spiked with cholesterol at different concentration levels yielded recoveries between 100% and 103%

An electrochemical immunosensor for testosterone using functionalized magnetic beads and screen-printed carbon electrodes.

A disposable electrochemical immunosensor using screen-printed carbon electrodes (SPCEs) and protein A-functionalized magnetic beads (MBs) was developed for the determination of testosterone. Anti-testosterone was immobilized onto MBs and a direct competitive immunoassay involving testosterone labeled with peroxidase (HRP) was performed. The resulting conjugate was trapped on the SPCE with a small magnet. Testosterone determination was carried out by amperometry at -0.2V upon H2O2 additions using hydroquinone (HQ) as the redox mediator. The experimental variables involved in the immunosensor response to testosterone were evaluated. Under the optimized conditions, a calibration plot for testosterone was obtained with a linear range between 5.0×10(-3) and 50 ng/mL (r=0.995). The detection limit was 1.7 pg/mL and the EC50 was 0.25±0.04 ng/mL. These characteristics are notably better than those achieved with other reported immunosensors. Furthermore, anti-testosterone/MBs conjugates were shown to be stable for at least 25 days. A good selectivity was also found against other steroid hormones. The usefulness of the immunosensor was demonstrated by analyzing human serum spiked with 1 and 10 ng/mL testosterone.

Disposable immunosensor for cortisol using functionalized magnetic particles.

A novel electrochemical immunosensor using screen-printed carbon electrodes and functionalized magnetic particles was developed for the determination of cortisol. Anti-cortisol antibody was immobilized onto protein A-modified magnetic particles and a direct competitive immunoassay involving cortisol antigen labeled with alkaline phosphatase (AP) was employed. The resulting conjugate was trapped on the surface of the screen-printed electrode with a small magnet. Cortisol quantification was accomplished by using 1-naphthyl phosphate as AP substrate and differential pulse voltammetry for the detection of the formed 1-naphthol. The variables involved in the preparation of the immunosensor and in the electrochemical detection reaction were optimized. The calibration plot obtained for cortisol exhibited a linear range between 5.0 x 10(-3) and 150 ng mL(-1) (r = 0.993). The limit of detection was 3.5 pg mL(-1), and the EC(50) was 0.19 ng mL(-1). These results demonstrate the high sensitivity achieved with this immunosensor design which compares favourably with other previous reports. The immunosensor also exhibited a high selectivity with respect to other corticosteroid compounds closely related to cortisol. The usefulness of the immunosensor for the analysis of real samples was demonstrated by analyzing certified human sera containing cortisol at two different concentration levels.