Polythiophenes and polythiophene-based composites in amperometric sensing

This overview of polythiophene-based materials provides a critical examination of meaningful examples of applications of similar electrode materials in electroanalysis. The advantages arising from the use of polythiophene derivatives in such an applicative context is discussed by considering the organic conductive material as such, and as one of the components of hybrid materials. The rationale at the basis of the combination of two or even more individual components into a hybrid material is discussed with reference to the active electrode processes and the consequent possible improvements of the electroanalytical performance. In this respect, study cases are presented considering different analytes chosen among those that are most frequently reported within the classes of organics and inorganics. The use of a polythiophene matrix to stably fix biological elements at the electrode surface for the development of catalytic biosensors and genosensors is also discussed. Finally, a few possible lines along which the next research in the field could be fruitfully pursued are outlined. Furthermore, the work still to be done to exploit the possibilities offered by novel products of organic synthesis, even along paths already traced in other fields of electrochemistry, is discussed.

Enhanced conductivity of a glassy carbon electrode modified with a graphene-doped film of layered double hydroxides for selectively sensing of dopamine

A strategy is presented for doping graphene into layered double hydroxide films (LDHs) as a means of improving charge transport of the LDH film in a modified glassy carbon electrode. This result in an enhanced electrocatalytic current for dopamine (DA) and a good separation of the potentials of DA, uric acid and ascorbic acid. Under selected conditions, the square wave voltammetric response of the electrode to DA is linear in the concentration range from 1.0 to 199???M even in the presence of 0.1?mM ascorbic acid, and the detection limit is 0.3???M at a signal-to-noise ratio of 3. The method was applied to the determination of DA in pharmaceutical injections with satisfactory results.

A glassy carbon electrode modified with graphene, gold nanoparticles and chitosan for ultrasensitive determination of lead(II)

We have modified a glassy carbon electrode by single-step electrodeposition of graphene (GR), gold nanoparticles (AgNPs), and chitosan (CS) directly from a solution containing graphene oxide, tetrachloroauric acid, and chitosan. The surface and electrochemical properties of the film-modified electrode were investigated by SEM and TEM images. The AuNPs have a diameter of about 20 nm and are uniformly dispersed in the matrix. Combining the advantages of GR (i.e., high surface area and conductivity), of AuNPs (excellent electrical conductivity) and CS (excellent film-forming ability and good water permeability), the hybrid film effectively enhances electron-transfer and promotes the response to lead(II) ion. Under the optimum conditions, a linear relationship exists between electrical current and the concentration of lead (II) ion in the range between 0.5 to 100 μg?L-1, with a detection limit of 1 ng?L-1 (at an SNR of 3). The electrode was successfully applied to the detection of lead(II) in spiked samples of river water.

Sensitive detection of enteropathogenic E. coli using a bfpA gene-based electrochemical sensor

We have developed a sensitive assay for enteropathogenic E. coli (EPEC) by integrating DNA extraction, specific polymerase chain reaction (PCR) and DNA detection using an electrode modified with the bundle-forming pilus (bfpA) structural gene. The PCR amplified products are captured on the electrode and hybridized with biotinylated detection probes to form a sandwich hybrid containing two biotinylated detection probes. The sandwich hybridization structure significantly combined the numerous streptavidin alkaline phosphatase on the electrode by biotin-streptavidin connectors. Electrochemical readout is based on dual signal amplification by both the sandwich hybridization structure and the enzyme. The electrode can satisfactorily discriminate complementary and mismatched oligonucleotides. Under optimal conditions, synthetic target DNA can be detected in the 1 pM to 10 nM concentration range, with a detection limit of 0.3 pM. EPEC can be quantified in the 10 to 10⁷ CFU mL^?1 levels within 3.5 h. The method also is believed to present a powerful platform for the screening of pathogenic microorganisms in clinical diagnostics, food safety and environmental monitoring.

Dispersive solid phase micro-extraction of dopamine from human serum using a nano-structured Ni-Al layered double hydroxide, and its direct determination by spectrofluorometry

We report on a simple method for dispersive solid-phase micro-extraction of dopamine (DA) from human serum. It is based on a layered double hydroxide (LDH) of nickel-aluminum, which acts as the extractant. DA is extracted at pH 8 using the LDH sol solution as a dispersed solid-phase extractor. The extracted DA is quantified by spectrofluorometry at 285?nm excitation and 315?nm emission wavelengths. A comparison of the fluorescence of DA in bulk solution and that of DA intercalated in the LDH revealed a nearly 5-fold improvement in intensity. Factors such as pH, concentration of LDH in the sol solution, and temperature were optimized. Under these conditions, the limit of detection is 0.015?μg?L^?1. The inter- and intra-day relative standard deviations for six replicate determinations of 1?μg?L^?1 DA were 1.7 and 1.1?%, respectively. The method was successfully applied to the determination of DA in human serum samples.

Sensitive detection of hydrogen peroxide in foodstuff using an organic�Cinorganic hybrid multilayer-functionalized graphene biosensing platform

We report on a new electrochemical biosensing strategy for the sensitive detection of hydrogen peroxide (H₂O₂) in foodstuff samples. It is based on a gold electrode modified with layer of graphene patterned with a multilayer made from an organic?Cinorganic hybrid nanomaterial. Initially, a layer of thionine (Th) was assembled on the surface of the graphene nanosheets, and these were then cast on the surface of the electrode for the alternate assembly of gold nanoparticles and horseradish peroxidase. The large surface-to-volume ratio and high conductivity of the nanosheets provides a benign microenvironment for the construction of the biosensor. The use of such a multilayer not only shortens the electron transfer pathway of the active center of the enzyme due to the presence of gold nanoparticles, but also enhances the electrocatalytic efficiency of the biosensor toward the reduction of H₂O₂. The electrochemical characteristics of the biosensor were studied by cyclic voltammetry and chronoamperometry. The number of layers, the operating potential, and the pH of the supporting electrolyte were optimized. Linear response is obtained for the range from 0.5???M to 1.8?mM of H₂O₂, the detection limit is 10 nM (at S/N?=?3), and 95% of the steady-state current is reached within 2?s. The method was applied to sense H₂O₂ in spiked sterilized milk and correlated excellently with the permanganate titration method.

Sensing water in organic solvent using a polyurethane-silica hybrid membrane doped with a luminescent ruthenium complex

We have prepared an ~1.4 μm thin hybrid film from polyurethane (PU) hydrogel and tetraethylorthosilicate (TEOS) by a sol–gel method, and have incorporated the red-luminescent ruthenium-tris-bipyridyl complex. At an optimized ratio of PU/TEOS (1.5:1; w/w) and annealing temperature (60 °C), the membrane sensor exhibits good capability to extract water from organic solvents but also can well retain the ruthenium dye. If contacted with water-containing organic solvents such as acetone or THF, both the luminescence intensity and wavelength change significantly. The response of luminescence intensity to the water fraction in organics is sigmoidal, which can be well fitted with a modified Stern-Volmer equation. The sensor works in the ranges of 0–6 % and 0–12 % (v/v) of water in acetone and THF, respectively, with detection limits of 0.13 % and 0.486 % (v/v).

Layered-double-hydroxide-modified electrodes: electroanalytical applications

Two-dimensional inorganic solids, such as layered double hydroxides (LDHs), also defined as anionic clays, have open structures and unique anion-exchange properties which make them very appropriate materials for the immobilization of anions and biomolecules that often bear an overall negative charge. This review aims to describe the important aspects and new developments of electrochemical sensors and biosensors based on LDHs, evidencing the research from our own laboratory and other groups. It is intended to provide an overview of the various types of chemically modified electrodes that have been developed with these 2D layered materials, along with the significant advances made over the last several years. In particular, we report the main methods used for the deposition of LDH films on different substrates, the conductive properties of these materials, the possibility to use them in the development of membranes for potentiometric anion analysis, the early analytical applications of chemically modified electrodes based on the ability of LDHs to preconcentrate redox-active anions and finally the most recent applications exploiting their electrocatalytic properties. Another promising application field of LDHs, when they are employed as host structures for enzymes, is biosensing, which is described considering glucose as an example.

A carbon nitride electrode for highly selective and sensitive determination of lead(II)

We have constructed a carbon nitride electrode modified with a bismuth film and show that it can be used for the electroanalysis of lead(II) by differential pulse anodic stripping voltammetry. The combination of such materials is shown to greatly improve the sensing capability of the electrode. Under the optimal conditions, the electrochemical response of the modified electrode is linearly related to the concentration of Pb(II) in the 6 – 1,000 nM concentration range (R = 0.9983). The detection limit is 2.0 pM (at an SNR of 3), and the sensitivity is 8 times better of that of respective graphite electrodes. The sensor enables rapid, highly sensitive, continuous, and environmentally friendly determination of trace levels of Pb(II) at affordable costs.

Selective microextraction of carbaryl and naproxen using organic–inorganic monolithic columns containing a double molecular imprint

We report on an organic–inorganic hybrid material that was double imprinted with the insecticide carbaryl and the anti-inflammatory drug naproxen by a single-step method and that can serve for selective microextraction of the two analytes. The materials, in the form of monolithic columns, were characterized by scanning electron microscopy and Fourier transform IR spectra. A simple, rapid and sensitive method was then developed for the simultaneous determination of carbaryl and naproxen in lettuce and river water using these columns for microextraction, HPLC for separation, and a diode array for UV detection. The limits of detection (at S/N?=?3) and quantification (at S/N?=?10) are in the ranges of 2.5 – 8.8 μg kg^?1 and 2.3 – 8.0 μg L^?1 for lettuce and Yangtze River water, respectively. The recoveries of this method range from 93.0 to 108 % (in case of analyzing lettuce and river water), and relative standard deviations are <8.9 %.

Ultrasensitive electrochemiluminescent detection of pentachlorophenol using a multiple amplification strategy based on a hybrid material made from quantum dots,graphene, and carbon nanotubes

We report on a highly sensitive and selective electrochemiluminescence (ECL) based method for the determination of pentachlorophenol (PCP). It is based on a new hybrid material composed of CdS quantum dots (QDs), graphene, and carbon nanotubes (CNTs), and uses peroxodisulfate as the coreactant. The use of this system results in a nearly 18-fold increase in ECL intensity. On interaction between PCP and the QDs, a decrease in ECL intensity is observed at PCP in a concentration as low as 1.0 pM and over a wide linear range (from 1.0 pM to 1.0 nM). The method is hardly affected by other chlorophenols and nitrophenols, and the electrode can be recycled.

Dopamine sensor based on a glassy carbon electrode modified with a reduced graphene oxide and palladium nanoparticles composite

We report on a sensitive electrochemical sensor for dopamine (DA) based on a glassy carbon electrode that was modified with a nanocomposite containing electrochemically reduced graphene oxide (RGO) and palladium nanoparticles (Pd-NPs). The composite was characterized by scanning electron microscopy, energy dispersive spectroscopy, and electrochemical impendence spectroscopy. The electrode can oxidize DA at lower potential (234 mV vs Ag/AgCl) than electrodes modified with RGO or Pd-NPs only. The response of the sensor to DA is linear in the 1–150 μM concentration range, and the detection limit is 0.233 μM. The sensor was applied to the determination of DA in commercial DA injection solutions.

Facile fabrication of polymer-inorganic hybrid particles with various morphologies by combination of hydrolytic condensation process with radiation seeded emulsion polymerization

A novel approach was proposed to the synthesis of poly(styrene-divinyl benzene-acrylic acid)/poly [3-(methacryloxy)propyl trimethoxysilane-styrene] [P(St-DVB-AA)/P(MPS-St)] hybrid particles. The morphologies of the particles could be tuned from raspberry-like to snowman-like by simply changing the feeding amount of second monomer or inorganic precursor. The fabricated raspberry-like ones could be modified to obtain hydrophobic surface with a contact angle up to 146°. And the snowman-like ones could be used as solid surfactant to stabilize water/styrene (W/St) mixtures, thus hierarchical porous materials could be obtained after the polymerization of monomer phase. The preliminary application of such soap-free block materials in oil-polluted water treatment was also investigated.

A sensitive and selective nitrite sensor based on a glassy carbon electrode modified with gold nanoparticles and sulfonated graphene

We describe a highly sensitive and selective amperometric sensor for the determination of nitrite. A glassy carbon electrode was modified with a composite made from gold nanoparticles (AuNPs) and sulfonated graphene (SG). The modified electrode displays excellent electrocatalytic activity in terms of nitrite oxidation by giving much higher peak currents (at even lower oxidation overpotential) than those found for the bare electrode, the AuNPs-modified electrode, and the SG-modified electrode. The sensor has a linear response in the 10 μM to 3.96 mM concentration range, a very good detection sensitivity (45.44 μA mM^?1), and a lower detection limit of 0.2 μM of nitrite. Most common ions and many environmental organic pollutants do not interfere. The sensor was successfully applied to the determination of nitrite in water samples, and the results were found to be consistent with the values obtained by spectrophotometry.

Electrochemical tyrosine sensor based on a glassy carbon electrode modified with a nanohybrid made from graphene oxide and multiwalled carbon nanotubes

We report on a glassy carbon electrode that was modified with a composite made from graphene oxide (GO) and multiwalled carbon nanotubes (MWCNT) that enables highly sensitive determination of L-tyrosine. The sensor was characterized by transmission electron microscopy and electrochemical impedance spectroscopy, and its electrochemical properties by cyclic voltammetry, chronocoulometry and differential pulse voltammetry. The GO/MWCNT hybrid exhibits strong catalytic activity toward the oxidation of L-tyrosine, with a well defined oxidation peak at 761 mV. The respective current serves as the analytical information and is proportional to the L-tyrosine concentration in two ranges of different slope (0.05 to 1.0 μM and 1.0 to 650.0 μM), with limits of detection and quantification as low as 4.4 nM and 14.7 nM, respectively. The method was successfully applied to the analysis of L-tyrosine in human body fluids. The excellent reproducibility, stability, sensitivity and selectivity are believed to be due to the combination of the electrocatalytic properties of both GO and MWCNT. They are making this hybrid electrode a potentially useful electrochemical sensing platform for bioanalysis.

Amperometric sensing of hydrogen peroxide using a glassy cabon electode modified with silver nanoparticles on poly(alizarin yellow R)

A sensitive amperometric sensor for hydrogen peroxide (HP) was constructed that is based on a glassy carbon electrode (GCE) modified with silver nanoparticles on poly(alizarin yellow R). The polymer was electropolymerized onto the surface of the GCE by cyclic voltammetry (CV), and the AgNPs were then electrodeposited onto its surface. The electrode was characterized by scanning electron microscopy and CV, and used for amperometric determination of HP. The electrode exhibits a favorable catalytic activity towards the reduction of HP, with a linear response range from 1.0???M to 450???M and a detection limit of 0.32???M. The sensor also displays high selectivity, excellent reproducibility, and good long-term stability.

Determination of thiourea using a carbon paste electrode decorated with copper oxide nanoparticles

We report on a novel sensor for the electrochemical determination of thiourea (TU). It is based on an active carbon paste electrode modified with copper oxide nanoparticles. The modified electrode and the electrochemical properties of thiourea on its surface were investigated using cyclic voltammetry and differential pulse voltammetry. Under optimized conditions, the detection limit is 20 μg?L^?1 of TU. The method was applied to the determination of thiourea in fruit juice, orange peel and industrial waste water.

Electrochemical aptasensor for the determination of bisphenol A in drinking water

We present an electrochemical aptasensor for rapid and ultrasensitive determination of the additive bisphenol A (BPA) and for screening drinking water for the presence of BPA. A specific aptamer against BPA and its complementary DNA probe were immobilized on the surface of a gold electrode via self-assembly and hybridization, respectively. The detection of BPA is mainly based on the competitive recognition of BPA by the immobilized aptamer on the surface of the electrode. The electrochemical aptasensor enables BPA to be detected in drinking water with a limit of detection as low as 0.284 pg?mL^?1 in less than 30 min. This extraordinary sensitivity makes the method a most powerful tool for on-site monitoring of water quality and food safety.

Electrochemical oxidation behavior of guanosine-5��-monophosphate on a glassy carbon electrode modified with a composite film of graphene and multi-walled carbon nanotubes, and its amperometric determination

The electrochemical oxidation of guanosine-5??-monophosphate (GMP) was studied with a glassy carbon electrode modified with a composite made from graphene and multi-walled carbon nanotubes. GMP undergoes an irreversible oxidation process at an oxidation peak potential of 987?mV in phosphate buffer solution. Compared to other electrodes, the oxidation peak current of GMP with this electrode was significantly increased, and the corresponding oxidation peak potential negatively shifted, thereby indicating that the modified material exhibited electrochemical catalytic activity towards GMP. Chronocoulometry demonstrates that the material also effectively increases the surface area of the electrode and increases the amount of GMP adsorbed. Under the optimum conditions, the oxidation current is proportional to the GMP concentration in the range from 0.1 to 59.7???M with a correlation coefficient of 0.9991. The detection limit is 0.025???M (at S/N?=?3).

Glassy carbon electrode modified with organic�Cinorganic pillared montmorillonites for voltammetric detection of mercury

A glassy carbon electrode modified with organic?Cinorganic pillared montmorillonite was used for voltammetric detection of mercury(II) in water. High sensitivity is obtained due to the use of the montmorillonites which displays outstanding capability in terms of adsorbing mercury ion due to its high specific surface and the presence of multiple binding sites. The experimental parameters and the effect of a chelating agent were optimized to further enhance sensitivity and selectivity. Linear calibration curves were obtained over the Hg(II) concentration range from 10 to 800???g?L^?1 for 5?min accumulation, with a detection limit of 1???g?L^?1. Simultaneous determination of Hg(II) and Cu(II) was also studied, and no interference was observed.