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We are reporting an innovative building-block for the development of biosensors based on the non-covalent functionalization of multi-walled carbon nanotubes (MWCNTs) with avidin (MWCNTs-avidin). In this work, at variance with previous reports, avidin has the double role of simultaneously being the exfoliating agent of MWCNTs and the platform for anchoring different biotinylated biomolecules. The optimum dispersion was obtained by sonicating for 5.0 min 0.50 mgmL -1 MWCNTs with 1.00 mgmL -1 avidin solution prepared in 50:50 v/v ethanol/water. As proof-of-concept, we immobilized biotinylated horseradish peroxidase (b-HRP) at glassy carbon electrodes (GCE) modified with MWCNTs-avidin to develop a hydrogen peroxide biosensor using hydroquinone as redox mediator. Surface plasmon resonance, electrochemical impedance spectroscopy, cyclic voltammetry and amperometry demonstrated that, even after the partial denaturation of avidin due to the drastic conditions used to functionalize the MWCNTs, it preserves the biorecognition properties and efficiently interacts with biotinylated horseradish peroxidase (b-HRP). The analytical characteristics of the resulting hydrogen peroxide biosensor are the following: linear range between 1.0 × 10 -6  M and 1.4 × 10 -5  M, sensitivity of (1.37 ± 0.04) x 10 5 μAM -1 , detection limit of 24 nM and reproducibility of 2.9%. The sensor was challenged with different samples, a mouthwash solution, human blood serum and milk, with very good performance., (Copyright © 2019 Elsevier B.V. All rights reserved.)

We report the quantification of promethazine (PMZ) using glassy carbon electrodes (GCE) modified with bamboo-like multi-walled carbon nanotubes (bCNT) dispersed in double stranded calf-thymus DNA (dsDNA) (GCE/bCNT-dsDNA). Cyclic voltammetry measurements demonstrated that PMZ presents a thin film-confined redox behavior at GCE/bCNT-dsDNA, opposite to the irreversibly-adsorbed behavior obtained at GCE modified with bCNT dispersed in ethanol (GCE/bCNT). Differential pulse voltammetry-adsorptive stripping with medium exchange experiments performed with GCE/bCNT-dsDNA and GCE modified with bCNTs dispersed in single-stranded calf-thymus DNA (ssDNA) confirmed that the interaction between PMZ and bCNT-dsDNA is mainly hydrophobic. These differences are due to the intercalation of PMZ within the dsDNA that supports the bCNTs, as evidenced from the bathochromic displacement of UV-Vis absorption spectra of PMZ and quantum dynamics calculations at DFTB level. The efficient accumulation of PMZ at GCE/bCNT-dsDNA made possible its sensitive quantification at nanomolar levels (sensitivity: (3.50±0.05)×10(8) μA·cm(-2)·M(-1) and detection limit: 23 nM). The biosensor was successfully used for the determination of PMZ in a pharmaceutical product with excellent correlation., (Copyright © 2014 Elsevier B.V. All rights reserved.)

This review present a critical comparison of the electrochemical behavior and analytical performance of glassy carbon electrodes (GCE) modified with carbon nanotubes (CNTs) dispersed in different polymers: polyethylenimine (PEI), PEI functionalized with dopamine (PEI-Do), polyhistidine (Polyhis), polylysine (Polylys), glucose oxidase (GOx) and double stranded calf-thymus DNA (dsDNA). The comparison is focused on the analysis of the influence of the sonication time, solvent, polymer/CNT ratio, and nature of the polymer on the efficiency of the dispersions and on the electrochemical behavior of the resulting modified electrodes. The results allow to conclude that an adequate selection of the polymers makes possible not only an efficient dispersion of CNTs but also, and even more important, the building of successful analytical platforms for the detection of different bioanalytes like NADH, glucose, DNA and dopamine., (Copyright © 2013 Elsevier B.V. All rights reserved.)

We report for the first time the use of double stranded calf-thymus DNA (dsDNA) to successfully disperse bamboo-like multi-walled carbon nanotubes (bCNT). The dispersion and the modified electrodes were studied by different spectroscopic, microscopic and electrochemical techniques. The drastic treatment for dispersing the bCNT (45min sonication in a 50% (v/v) ethanol:water solution), produces a partial denaturation and a decrease in the length of dsDNA that facilitates the dispersion of CNT and makes possible an efficient electron transfer of guanine residues to the electrode. A critical analysis of the influence of different experimental conditions on the efficiency of the dispersion and on the performance of glassy carbon electrodes (GCE) modified with bCNT-dsDNA dispersion is also reported. The electron transfer of redox probes and guanine residues was more efficient at GCE modified with bCNT dispersed in dsDNA than at GCE modified with hollow CNT (hCNT) dispersed in dsDNA, demonstrating the importance of the presence of bCNT., (Copyright © 2013 Elsevier B.V. All rights reserved.)

We report for the first time the use of polyhistidine (Polyhis) to efficiently disperse multiwall carbon nanotubes (MWCNTs). The optimum dispersion MWCNT-Polyhis was obtained by sonicating for 30 min 1.0 mg mL(-1) MWCNTs in 0.25 mg mL(-1) Polyhis solution prepared in 75:25 (v/v) ethanol/0.200 M acetate buffer solution pH 5.00. The dispersion was characterized by scanning electron microscopy, and by cyclic voltammetry and amperometry using ascorbic acid as redox marker. The modification of glassy carbon electrodes with MWCNT-Polyhis produces a drastic decrease in the overvoltage for the oxidation of ascorbic acid (580 mV) at variance with the response observed at glassy carbon electrodes modified just with Polyhis, where the charge transfer is more difficult due to the blocking effect of the polymer. The reproducibility for the sensitivities obtained after 10 successive calibration plots using the same surface was 6.3%. The MWCNT-modified glassy carbon electrode demonstrated to be highly stable since after 45 days storage at room temperature the response was 94.0% of the original. The glassy carbon electrode modified with MWCNT-Polyhis dispersion was successfully used to quantify dopamine or uric acid at nanomolar levels, even in the presence of large excess of ascorbic acid. Determinations of uric acid in human blood serum samples demonstrated a very good correlation with the value reported by Wienner laboratory., (Copyright © 2011 Elsevier B.V. All rights reserved.)

This work reports on the performance of carbon nanotube modified screen-printed electrodes (SPE-MWCNT) for the selective determination of dopamine (DA) in the presence of ascorbic acid (AA) by adsorptive stripping voltammetry (AdSV). Several operating conditions and parameters were examined including the electrochemical pre-treatment and the previous AA interaction and DA accumulation in the presence AA at physiological conditions. Under the chosen conditions, DA peak current of differential pulse voltammograms increases linearly with DA concentration in the range of 5.0 x 10(-8) to 1.0 x 10(-6) mol L(-1) with a limit of detection of 1.5 x 10(-8) mol L(-1) in connection with 600s accumulation time. The sensitivity obtained for DA was independent from the presence or absence of AA; therefore, the proposed method can be readily applied to detect DA in real samples. The proposed methodology was successfully used for the quantification of DA in urine samples., (Copyright (c) 2009 Elsevier B.V. All rights reserved.)

This work reports the advantages of a label free electrochemical aptasensor for the detection of lysozyme. The biorecognition platform was obtained by the adsorption of the aptamer on the surface of a carbon paste electrode (CPE) previously blocked with mouse immunoglobulin under controlled-potential conditions. The recognition event was detected from the decrease in the guanine and adenine electro-oxidation signals produced as a consequence of the molecular interaction between the aptamer and lysozyme. The biosensing platform demonstrated to be highly selective even in the presence of large excess (9-fold) of bovine serum albumin, cytochrome C and myoglobin. The reproducibility for 10 repetitive determinations of 10.0 mg L(-1) lysozyme solution was 5.1% and 6.8% for guanine and adenine electro-oxidation signals, respectively. The detection limits of the aptasensor were 36.0 nmol L(-1) (if considering guanine signal) and 18.0 nmol L(-1) (if taking adenine oxidation current). This new sensing approach represents an interesting and promising alternative for the electrochemical quantification of lysozyme.

The aim of this review is to summarize the most relevant contributions in the development of electrochemical (bio)sensors based on carbon nanotubes in the last years. Since the first application of carbon nanotubes in the preparation of an electrochemical sensor, an increasing number of publications involving carbon nanotubes-based sensors have been reported, demonstrating that the particular structure of carbon nanotubes and their unique properties make them a very attractive material for the design of electrochemical biosensors. The advantages of carbon nanotubes to promote different electron transfer reactions, in special those related to biomolecules; the different strategies for constructing carbon nanotubes-based electrochemical sensors, their analytical performance and future prospects are discussed in this article.

This work reports the advantages of using glassy carbon electrodes (GCEs) modified with multi-wall carbon nanotubes (CNT) dispersed in polyethylenimine (PEI) as detectors in flow injection and capillary electrophoresis. The presence of the dispersion of CNT in PEI at the electrode surface allows the highly sensitive and reproducible determination of hydrogen peroxide, different neurotransmitters (dopamine (D) and its metabolite dopac, epinephrine (E), norepinephrine (NE)), phenolic compounds (phenol (P), 3-chlorophenol (3-CP) and 2,3-dichlorophenol (2,3CP)) and herbicides (amitrol). Sensitivities enhancements of 150 and 140 folds compared to GCE were observed for hydrogen peroxide and amitrol, respectively. One of the most remarkable properties of the resulting electrode is the antifouling effect of the CNT/PEI layer. No passivation was observed either for successive additions (30) or continuous flow (for 30 min) of the compounds under investigation, even dopac or phenol. A critical comparison of the amperometric and voltammetric signal of these different analytes at bare- and PEI-modified glassy carbon electrodes and pyrolytic graphite electrodes is also included, demonstrating that the superior performance of CNT is mainly due to their unique electrochemical properties. Glassy carbon electrodes modified with CNT-PEI dispersion also show an excellent performance as amperometric detector in the electrophoretic separation of phenolic compounds and neurotransmitters making possible highly sensitive and reproducible determinations.

This work reports on the analytical performance of composites obtained by dispersing copper microparticles and multi-wall carbon nanotubes within a mineral oil binder (CNTPE-Cu) for the determination of amino acids and albumin. The strong complexing activity of amino acids towards copper makes possible an important improvement in the sensitivity for the determination of amino acids and albumin. This new electrode permits the highly sensitive amperometric detection of amino acids, even the non-electroactive ones, at very low potentials (0.000V) and physiological pH (phosphate buffer solution pH 7.40). The response of the electrode is highly dependent on the amount of copper, demonstrating the crucial role of the metal in the analytical performance of the sensor. The best analytical performance is obtained for the electrode containing 6.0% (w/w) copper. The resulting sensor shows a fast response (7s) and a sensitivity that depends on the nature of the amino acid. The electrode surface demonstrates an excellent resistance to surface fouling, with R.S.D. of 4% for the sensitivities of 10 successive calibration plots. Albumin is determined with CNTPE-Cu using a protocol based on the accumulation of the protein for 10min at -0.100V, followed by the square-wave voltammetric analysis. The quantification of albumin concentration in lyophilized control serum gives excellent agreement with the classical spectrophotometric methodology and with the value informed for the supplier.

We are proposing for the first time the use of a Nafion/multi-walled carbon nanotubes dispersion deposited on glassy carbon electrodes (GCE) as a new platform for developing enzymatic biosensors based on the self-assembling of a chitosan derivative and different oxidases. The electrodes are obtained by deposition of a layer of Nafion/multi-wall carbon nanotubes dispersion on glassy carbon electrodes, followed by the adsorption of a chitosan derivative as polycation and glucose oxidase, l-aminoacid oxidase or polyphenol oxidase, as polyanions and biorecognition elements. The optimum configuration for glucose biosensors has allowed a highly sensitive (sensitivity=(0.28+/-0.02)muAmM(-1), r=0.997), fast (4s in reaching the maximum response), and highly selective (0% interference of ascorbic acid and uric acid at maximum physiological levels) glucose quantification at 0.700V with detection and quantification limits of 0.035 and 0.107mM, respectively. The repetitivity for 10 measurements was 5.5%, while the reproducibility was 8.4% for eight electrodes. The potentiality of the new platform was clearly demonstrated by using the carbon nanotubes/Nafion layer as a platform for the self-assembling of l-aminoacid oxidase and polyphenol oxidase. Therefore, the platform we are proposing here, that combines the advantages of nanostructured materials with those of the layer-by-layer self-assembling of polyelectrolytes, opens the doors to new and exciting possibilities for the development of enzymatic and affinity biosensors using different transdution modes.

The work proposed here deals with the design and characterization of biorecognition layers for the amperometric glucose determination based on the self-assembling of new chitosan derivatives, Nafion and glucose oxidase onto thiolated gold electrodes. The supramolecular multistructure is obtained by deposition of a layer of chitosan derivative (quaternized or hydrophobic) onto the gold surface modified with the sodium salt of 3-mercapto-1-propansulfonic acid, followed by the deposition of a layer of Nafion (as anti-interference barrier) and by the alternate deposition of the chitosan derivative and glucose oxidase (as biocatalytic layer). The influence of the deposition time and concentration of polyelectrolytes, organization and number of layers, and nature of the chitosan derivative on the sensitivity and selectivity of the bioelectrode is examined and optimized in order to obtain a rational design of the biosensor. The system is studied electrochemically from the oxidation at 0.700 V of the hydrogen peroxide enzymatically generated using gold as substrate, and spectrophotometrically from the protein absorption at 277 nm using quartz as substrate. The selected biosensor containing five quaternized chitosan/glucose oxidase bilayers exhibits very good analytical performance with a sensitive ((4.9+/-0.2) x 10(2) nA mM(-1)) and highly selective response (0% interference for maximum physiological levels of ascorbic acid and uric acid), demonstrating that the alternate electrostatic adsorption of conveniently selected polyelectrolytes allows noticeable improvements in the selectivity and sensitivity of a biosensor.

In this work we report on the successful use of a composite prepared by dispersion of multi-wall carbon nanotubes (1-5 microm length, 20-50 nm diameter) and copper microparticles within mineral oil as detector for amino acids quantification in flow injection analysis and capillary electrophoresis. The resulting electrode displays a highly sensitive amperometric detection of amino acids, based on the copper dissolution facilitated by the strong activity of amino acids as ligands of Cu(II). The sensor makes possible the detection of amino acids, electroactive or not, at very low potentials (0.000 V) and physiological pH. A correlation between the sensitivity for the amino acids and the amount of copper within the composite is observed, demonstrating the importance of the metal in the sensor response. The best analytical performance is obtained for the electrode containing 12.0% (w/w) copper. The excellent results obtained with the carbon nanotube paste electrodes containing copper (CNTPE-Cu) as detector in flow systems makes them an interesting alternative for further analytical applications involving different bioanalytes.

In this work, we demonstrate for the first time that 4-methyl-5-nitrocatechol (4M5NC) and 2,4,5-trihydroxytoluene (2,4,5-THT), two compounds obtained from the 2,4-DNT biodegradation are recognized by polyphenol oxidase as substrates. An amperometric biosensor is described for detecting these compounds and for evaluating the efficiency of the 2,4-DNT conversion into 4M5NC in the presence of bacteria able to produce the 2,4-DNT-biotransformation. The biosensor format involves the immobilization of polyphenol oxidase into a composite matrix made of glassy carbon microspheres and mineral oil. The biosensor demonstrated to be highly sensitive for the quantification of 4M5NC and 2,4,5-THT. The analytical parameters for 4M5NC are the following: sensitivity of (7.5+/-0.1)x10(5)nAM(-1), linear range between 1.0x10(-5) and 8.4x10(-5)M, and detection limit of 4.7x10(-6)M. The sensitivity for the determination of 2,4,5-THT is (6.2+/-0.6)x10(6)nAM(-1), with a linear range between 1.0x10(-6) and 5.8x10(-6)M, and a detection limit of 2.0x10(-7). Under the experimental conditions, it was possible to selectively quantify 4M5NC even in the presence of a large excess of 2,4-DNT. The suitability of the biosensor for detecting the efficiency of 2,4-DNT biotransformation into 4M5NC is demonstrated and compared with HPLC-spectrophotometric detection, with very good correlation. This biosensor holds great promise for decentralized environmental testing of 2,4-DNT.

The performance of amperometric glucose biosensors based on the dispersion of glucose oxidase (GOx) and copper oxide within a classical carbon (graphite) paste composite is reported in this work. Copper oxide promotes an excellent electrocatalytic activity towards the oxidation and reduction of hydrogen peroxide, allowing a large decrease in the oxidation and reduction overpotentials, as well as an important enhancement of the corresponding currents. Therefore, it is possible to perform the glucose biosensing at low potentials where there is no interference even in large excess of ascorbic acid, uric acid or acetaminophen. The influence of the copper oxide and glucose oxidase content in the paste on the analytical performance of the bioelectrode is discussed. The resulting biosensor shows a fast response, a linear relationship between current and glucose concentration up to 1.35 x 10(-2) M (2.43 g L(-1)) and a detection limit of 2.0 x 10(-5) M. The effect of the presence of the enzyme in the composite material on the dispersion of the copper oxide particles is also discussed.

The affinity of mushroom polyphenol oxidase (PPO) towards gentisic acid (GA), a metabolite of acetyl salicylic acid (ASA), is demonstrated by spectrophotometry and by electrochemical techniques. The enzyme can selectively recognize GA even in the presence of large excess of ASA and its metabolic derivatives (salicylic acid (SA) and salicyluric acid (SUA)). At -0.150 V, the sensitivity is (6.1+/-0.1)x10(4) NAM(-1), the response is linear up to 2.0x10(-4) M and the detection limit is 5.0x10(-5) M. The kinetic parameters, obtained from Eadie-Hofstee plots, are I(max)=51.4 nA and K(m)(app)=6.7x10(-4) M.

The determination of salicylic acid was carried out by reaction of the drug with copper carbonate entrapped in a polymeric material in a solid-phase reactor; the released cupric ions were monitored by flame atomic absorption at 324.8 nm. The calibration graph is linear over the range 4.0-75 mug ml(-1) of salicylic acid, with a relative standard deviation of less than 1.5% and a sample throughout of 257 h(-1). The influence of foreign compounds was studied and the method was applied to the determination of salicylic acid content in two different pharmaceutical formulations.

MCA is a tissue adhesive which can be delivered transcervically to the Fallopian tubes by means of the FEMCEPT device. In the patients treated with this system, both prior to hysterectomy and on an ambulatory basis, there have been no significant complications or side effects. In the most recent series of ambulatory patients treated with the REMCEPT-MCA system, the bilateral tubal closure rate was 78%.