We are presenting an electrochemical immunosensor for the determination of the β-agonist and food additive ractopamine. A glassy carbon electrode (GCE) was modified with gold nanoparticles and a film of a composite made from poly(arginine) and multi-walled carbon nanotubes. Antibody against ractopamine was immobilized on the surface of the modified GCE which then was blocked with bovine serum albumin. The assembly of the immunosensor was followed by electrochemical impedance spectroscopy. Results demonstrated that the semicircle diameter increases, indicating that the film formed on the surface hinders electron transfer due to formation of the antibody-antigen complex on the modified electrode. Under optimal conditions, the peak current obtained by differential pulse voltammetry decreases linearly with increasing ractopamine concentrations in the 0.1 nmol•L−1 to 1 μmol•L−1 concentration range. The lower detection limit is 0.1 nmol•L−1. The sensor displays good stability and reproducibility. The method was applied to the analysis of spiked swine feed samples and gave satisfactory results.
Immunoassay for ractopamine based on glassy carbon electrode modified with gold nanoparticles and a film of a composite made from poly (arginine) and multi-walled carbon nanotubes was proposed. Under optimal conditions, the peak currents obtained by differential pulse voltammetry decreases linearly with increasing ractopamine concentrations in the 0.1 nmol•L−1 to 1 μmol•L−1 concentration range. The detection limit is 0.1 nmol•L−1.
We demonstrate the application of an ionic liquid-based ferrofluid to the dispersive solid phase extraction of lead(II) using PAN as the chelator. The ionic liquid contains silica nanoparticles with a magnetic core as the dispersion medium, and its use results in improved stability of the colloidal dispersion and a complete extraction of lead(II) within a few seconds. In addition, there is no need for centrifugation. Specifically, the effect of different variables on the extraction of lead(II) was studied using an experimental design. Lead(II) was quantified by AAS. Under optimized conditions, the calibration graph for lead(II) is linear in the range from 5 to 372 μg L−1, the relative standard deviation is 1.34 % (for n = 7), the limit of detection is 1.66 μg L−1, and the enrichment factor is 200. The maximum adsorption capacity of sorbent was calculated to be 10.7 mg g−1, and adsorption follows a Langmuir isotherm.
A schematic view of D-SPE experimental set up. We demonstrate the application of an ionic liquid-based ferrofluid to the dispersive solid phase extraction of lead(II) using PAN as the chelator. The ionic liquid contains silica nanoparticles with a magnetic core as the dispersion medium
The authors describe an efficient method for microextraction and preconcentration of trace quantities of cationic nitrogen compounds, specifically of anilines. It relies on a combination of electrochemically controlled solid-phase microextraction and on-line in-tube solid-phase microextraction (SPME) using polypyrrole-coated capillaries. Nanostructured polypyrrole was electrically deposited on the inner surface of a stainless steel tube and used as the extraction phase. It also acts as a polypyrrole electrode that was used as a cation exchanger, and a platinum electrode that was used as the anode. The solution to be extracted is passed over the inner surface of the polypyrrole electrode, upon which cations are extracted by applying a negative potential under flow conditions. This method represents an ideal technique for SPME of protonated anilines because it is fast, easily automated, solvent-free, and inexpensive. Under optimal conditions, the limits of detection are in the 0.10–0.30 μg L‾1 range. The method works in the 0.10 to 300 μg L‾1 concentration range. The inter- and intra-assay precisions (RSD%; for n = 3) range from 5.1 to 7.5 % and from 4.7 to 6.0 % at the concentration levels of 2, 10 and 20 μg L‾1, respectively. The EC-in-tube SPME method was successfully applied to the analysis of methyl-, 4-chloro-, 3-chloro and 3,4-dichloroanilines in (spiked) water samples.
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We have studied the direct electrochemistry of glucose oxidase (GOx) immobilized on electrochemically fabricated graphite nanosheets (GNs) and zinc oxide nanoparticles (ZnO) that were deposited on a screen printed carbon electrode (SPCE). The GNs/ZnO composite was characterized by using scanning electron microscopy and elemental analysis. The GOx immobilized on the modified electrode shows a well-defined redox couple at a formal potential of −0.4 V. The enhanced direct electrochemistry of GOx (compared to electrodes without ZnO or without GNs) indicates a fast electron transfer at this kind of electrode, with a heterogeneous electron transfer rate constant (Ks) of 3.75 s−1. The fast electron transfer is attributed to the high conductivity and large edge plane defects of GNs and good conductivity of ZnO-NPs. The modified electrode displays a linear response to glucose in concentrations from 0.3 to 4.5 mM, and the sensitivity is 30.07 μA mM−1 cm−2. The sensor exhibits a high selectivity, good repeatability and reproducibility, and long term stability.
Graphical representation for the fabrication of GNs/ZnO composite modified SPCE and the immobilization of GOx
We have combined the molecular imprinting and the layer-by-layer assembly techniques to obtain molecularly imprint polymers (MIPs) for the electrochemical determination of p-nitrophenol (p-NPh). Silica microspheres functionalized with thiol groups and gold nanoparticles (Au-NPs) were assembled on a gold electrode surface layer by layer. The electrode was then immersed into a solution of pyrrole and p-NPh (the template), and electropolymerization led to the creation of a polymer-modified surface. After the removal of the silica spheres and the template, electrochemical impedance spectroscopy and differential pulse voltammetry (DPV) were employed to characterize the surface. The results demonstrated the successful fabrication of macroporous MIPs embedded with Au-NPs on the gold electrode. The effects of monomer concentration and scan rate on the performance of the electrode were optimized. Excellent recognition capacity is found for p-NPh over chemically similar species. The DPV peak current is linearly related to concentration of p-NPh in the 0.1 μM to 1.4 mM range, with a 0.1 μM limit of detection (at S/N = 3).
Molecularly imprinted polymers (MIPs) and nanomaterials were combined to prepare a novel macroporous structured MIPs based electrochemical sensor for the investigation of an environmental pollutant, p-nitrophenol (p-NPh). The sensor exhibited a fast binding dynamics, good specific adsorption capacities, and high selective recognition to p-NPh.
We report on the capillary electrophoretic behavior of citrate-capped gold and silver nanoparticles in aqueous medium when applying a ligand-exchange surface reaction with thiols. Gold nanoparticles (AuNPs) and silver nanoparticles (AgNPs) of similar size (39 ± 6 and 41 ± 7 nm, respectively) and shape were synthesized, covered with a citrate shell, and characterized by microscopic and spectroscopic techniques. The analysis of these NPs by CE was accomplished by using a buffer solution (pH 9.7; 40 mM SDS, 10 mM CAPS; 0.1 % methanol) containing the anions of thioctic acid or thiomalic acid. These are capable of differently interacting with the surface of the AuNPs and AgNPs and thus introducing additional negative charges. This results in different migration times due to the formation of differently charged nanoparticles.
Capillary electrophoretic behavior of citrate-capped gold and silver nanoparticles (NPs) in aqueous medium when applying a ligand-exchange surface reaction with thiols (thioctic and thiomalic acids), which introduces additional negative charges, has been studied
We describe an anodic stripping voltammetric (ASV) method for glucose sensing that widely expands the typical amperometric i-t response of glucose sensors. The electrode is based on a working electrode consisting of a glassy carbon electrode modified with Pt-Pd nanoparticles (NPs; in an atomic ratio of 3:1) on a reduced graphene oxide (rGO) support. The material was prepared via the spontaneous redox reaction between rGO, PdCl4 2− and PtCl4 2− without any additional reductant or surfactant. Unlike known Pt-based sensors, the use of Pt3Pd NPs results in an ultrasensitive ASV approach for sensing glucose even at near-neutral pH values. If operated at a working voltage as low as 0.06 V (vs. SCE), the modified electrode can detect glucose in the 2 nM to 300 μM concentration range. The lowest detectable concentration is 2 nM which is much lower than the LODs obtained with other amperometric i-t type sensing approaches, most of which have LODs at a μM level. The sensor is not interfered by the presence of 0.1 M of NaCl.
We describe an anodic stripping voltammetric method for glucose sensing that widely expands the typical amperometric i-t response of glucose sensors (2 nM to 300 μM). The electrode is based on a glassy carbon electrode modified with Pt-Pd nanoparticles on a reduced graphene oxide (rGO) support.
We describe an electrochemical sensor for simultaneous determination of hydroquinone (HQ) and catechol (CC). A glassy carbon electrode (GCE) was modified with gold nanoparticles, L-cysteine, and ZnS/NiS@ZnS quantum dots using a layer-by-layer technique. The materials were characterized by X-ray diffractometry, field emission scanning electron microscopy, and electrochemical impedance and Fourier transform infrared spectroscopy. Cyclic voltammetry and differential pulse voltammetry revealed this modified GCE to represent a highly sensitive sensor for the simultaneous determination of HQ and CC. The anodic peak current for HQ at a working voltage of 80 mV (vs. Ag/AgCl) is related to its concentration in the 0.1 to 300 μM range (even in the presence of 0.1 mM of CC). The anodic peak current for CC at a working voltage of 184 mV is related to its concentration in the 0.5 to 400 μM range (even in the presence of 0.1 mM of HQ). The detection limits (at an S/N ratio of 3) are 24 and 71 nM for HQ and CC, respectively. The modified GCE was successfully applied to the determination of HQ and CC in aqueous solutions and gave satisfactory results.
A glassy carbon electrode was modified with gold nanoparticles, ZnS/NiS@ZnS quantum dots and L-cysteine and used for simultaneous determination of hydroquinone and catechol.
A fluorescent probe for the sensitive and selective determination of sulfide ions is presented. It is based on the use of graphene quantum dots (GQDs) which emit strong and stable blue fluorescence even at high ionic strength. Copper(II) ions cause aggregation of the GQDs and thereby quench fluorescence. The GQDs-Cu(II) aggregates can be dissociated by adding sulfide ions, and this results in fluorescence turn on. The change of fluorescence intensity is proportional to the concentration of sulfide ions. Under optimal conditions, the increase in fluorescence intensity on addition of sulfide ions is linearly related (r 2 = 0.9943) to the concentration of sulfide ions in the range from 0.20 to 20 μM, and the limit of detection is 0.10 μM (at 3 σ/s). The fluorescent probe is highly selective for sulfide ions over some potentially interfering ions. The method was successfully applied to the determination of sulfide ions in real water samples and gave recoveries between 103.0 and 113.0 %.
Graphene quantum dots (GQDs) emit strong blue fluorescence which, however, is quenched by copper(II) ions due to the formation of GQDs-Cu(II) aggregates. Fluorescence is recovered by sulfide ions due to the dissociation of GQDs-Cu(II) aggregates.
A nanocomposite consisting of coral-like gold nanostructures on reduced graphene oxide (RGO) was synthesized with the assistance of dimethylbiguanide (DMBG). It was then fabricated on a glassy carbon electrode, coating with cysteamine in order to enable the immobilization of acetylcholinesterase (AChE) as a model enzyme whose activity of hydrolyzing the substrate of acetylthiocholine is inhibited by the pesticide triazophos. The biosensor has response to acetylthiocholine in the 0.3 ~ 300 μM concentration range at 0.65 V (vs. SCE). The inhibition of the enzyme by triazophos can be determined in concentrations of up to 210 ppb, with a detection limit of 0.35 ppb of triazophos (S/N = 3). The biosensor is highly reproducible and acceptably stable.
Coral-like gold nanostructures supported on reduced graphene oxide were synthesized with the assistance of dimethylbiguanide to fabricate an acetylcholinesterase (AChE) biosensor, which exhibited high reproducibility and good stability, providing a good platform for the detection of organophosphorus pesticides.
We report on an electrochemical method for the determination of the activity of trypsin. A multi-functional substrate peptide (HHHAKSSATGGC-HS) is designed and immobilized on a gold electrode. The three His residues in the N-terminal are able to recruit thionine-loaded graphene oxide (GO/thionine), a nanocover adopted for signal amplification. Once the peptide is cleaved under enzymatic catalysis by trypsin (cleavage site: Lys residue), the His residues leave the electrode, and the GO/thionine cannot cover the peptide-modified electrode anymore. Thus, the changes of the electrochemical signal of thionine, typically acquired at a voltage of -0.35 V, can be used to determine the activity of trypsin. A detection range of 1 × 10−4 to 1 U, with a detection limit of 3.3 × 10−5 U, can be achieved, which is better than some currently available methods. In addition, the method is highly specific, facile, and has the potential for the detection of trypsin-like proteases.
Graphene oxide was adopted as a nanocover for the development of a sensitive electrochemical method to detect the activity of trypsin.
We describe a sensitive and selective biosensor for the environmental metabolite 2-hydroxyfluorene (2-HOFlu). It is based on electrochemical impedance spectroscopy and was obtained by assembling a thiolated single-stranded DNA on a gold electrode via S-Au covalent bonding. It is then transformed to a K+-stabilized G-quadruplex-hemin complex which exhibits peroxidase-like activity to catalyze the oxidation of 2-HOFlu by H2O2. This results in the formation of insoluble products that are precipitated on the gold electrode. As a result, the charge transfer resistance (R CT) between the solution and the electrode surface is strongly increased within 10 min as demonstrated by using the ferro/ferricyanide system as a redox probe. The difference in the charge transfer resistances (ΔR CT) before and after incubation of the DNA film with 2-HOFlu and H2O2 serves as the signal for the quantitation of 2-HOFlu with a 1.2. nM detection limit in water of pH 7.4. The assay is highly selective over other selected fluorene derivatives. It was exploited to determine 2-HOFlu in spiked lake water samples where it displayed a detection limit of 3.6 nM. Conceivably, this method has a wide scope in that it may be applied to other analytes for which respective G-quadruplexes are available.
A G-quadruplex DNAzyme based impedimetric biosensor for sensitive detection of 2-hydroxyfluorene using hemin as a peroxidase enzyme mimic was constructed with a detection limit of 1.2 nM in water and 3.6 nM in spiked lake water samples.
This article describes an electrochemical sensor for the dye additive Sunset Yellow (SY). It consists of a carbon paste electrode modified with nanostructured resorcinol-formaldehyde (RF) resin. The RF resin warrants strong signal enhancement and a strongly increased oxidation peak currents of SY at 0.66 V (vs. SCE). The effects of pH value, amount of RF polymer, accumulation potential and time were optimized. The sensor has a linear response to SY in the 0.3 to 125 nM concentration range, and the limit of detection is 0.09 nM after a 2-min accumulation time. The electrode was applied to the analysis of samples of wastewater and drinks, and the results are consistent with those obtained by HPLC.
Nanostructured resorcinol-formaldehyde (RF) resin was prepared and used as a material for electrochemical determination of Sunset Yellow.
Alloy nanoparticles of the type PtxFe (where x is 1, 2 or 3) were synthesized by coreduction with sodium borohydride in the presence of carbon acting as a chemical support. The resulting nanocomposites were characterized by scanning electron microscopy and X-ray diffraction. The nanocomposite was placed on a glassy carbon electrode, and electrochemical measurements indicated an excellent catalytic activity for the oxidation of glucose even a near-neutral pH values and at a working voltage as low as 50 mV (vs. SCE). Under optimized conditions, the sensor responds to glucose in the 10.0 μM to 18.9 mM concentration range and with a 3.0 μM detection limit (at an S/N ratio of 3). Interferences by ascorbic acid, uric acid, fructose, acetamidophenol and chloride ions are negligible.
Nonenzymatic sensing of glucose is demonstrated at neutral pH values and low working potential using a glassy carbon electrode modified with platinum-iron alloy nanoparticles on a carbon support.
This work describes a novel polyaniline-magnetite nanocomposite and its application to the preconcentration of Cr(VI) anions. The material was obtained by oxidative polymerization of aniline in the presence of magnetite nanoparticles. The parameters affecting preconcentration were optimized by a Box-Behnken design through response surface methodology. Extraction time, amount of magnetic sorbent and pH value were selected as the main factors affecting sorption. The sorption capacity of the sorbent for Cr(VI) is 54 mg g−1. The type, volume and concentration of the eluents, and the elution time were selected as main factors in the optimization study of the elution step. Following sorption and elution, the Cr(VI) ions were reacted with diphenylcarbazide, and the resulting dye was quantified by HPLC with optical detection at 546 nm. The limit of detection is 0.1 μg L−1, and all the relative standard deviations are <6.3 %. The nanocomposite was successfully applied to the rapid extraction and determination of trace quantities of Cr(VI) ions in spiked water samples.
A schematic procedure of magnetic solid phase extraction
Hemoglobin (Hb) has been demonstrated to endow electrochemical sensors with pH-switchable response because of the presence of carboxyl and amino groups. Hb was deposited in a chitosan matrix on a glassy carbon electrode (GCE) that was previously coated with clustered gold nanoparticles (Au-NPs) by electrodeposition. The switching behavior is active (“on”) to the negatively charged probe [Fe(CN)6 3−] at pH 4.0, but inactive (“off”) to the probe at pH 8.0. This switch is fully reversible by simply changing the pH value of the solution and can be applied for pH-controlled reversible electrochemical reduction of H2O2 catalyzed by Hb. The modified electrode was tested for its response to the different electroactive probes. The response to these species strongly depends on pH which was cycled between 4 and 8. The effect is also attributed to the presence of pH dependent charges on the surface of the electrode which resulted in either electrostatic attraction or repulsion of the electroactive probes. The presence of Hb, in turn, enhances the pH-controllable response, and the electrodeposited Au-NPs improve the capability of switching. This study reveals the potential of protein based pH-switchable materials and also provides a simple and effective strategy for fabrication of switchable chemical sensors as exemplified in a pH-controllable electrode for hydrogen peroxide.
A pH “on-off” switchable nanobiosensor was fabricated by casting a chitosan-hemoglobin biocomposite onto nano-gold electrode. This composite film exhibits not only excellent pH-responsive on (pH 4.0)-off (pH 8.0) behavior but also excellent pH-tunable on-off bioelectrocatalysis of H2O2.
We report on a new electrochemical immunosensor for the carcinoembryonic antigen (CEA; a model analyte). First, poly(o-phenylenediamine) nanospheres (PPDNSs) were synthesized by using a wet-chemistry method. The nanospheres were utilized as the support for immobilizing horseradish peroxidase-labeled polyclonal rabbit anti-human CEA antibody (HRP-anti-CEA) on a pretreated glassy carbon electrode (GCE) using glutaraldehyde as a crosslinker. In the presence of target CEA, an antigen-antibody immunocomplex formed on the electrode. This results in a partial inhibition of the active center of HRP and decreases the activity of HRP in terms of H2O2 reduction. The performance and factors influencing the performance of the immunoelectrode were studied. Under optimal conditions, the reduction current obtained from the anti-CEA-conjugated HRP (best at a working voltage of −265 mV vs. Ag/AgCl) is proportional to the CEA concentration in the 0.01 to 60 ng mL−1 range, with a detection limit of 3.2 pg mL−1. Non-specific adsorption was not observed. Relative standard deviations for intra-assay and inter-assay are <8.3 % and <9.7 %, respectively. The method was applied to the analysis of nine human serum samples, and a good relationship was found between the electrochemical immunoassay and the commercialized ELISA kit for human CEA.
A new electrochemical immunosensor based on poly(o-phenylenediamine) nanospheres was developed for the rapid detection of carcinoembryonic antigen via the inhibition of enzymatic activity.
We report on the use of quercetin-functionalized gold nanoparticles (QC-AuNPs) as a colorimetric probe for the amino acids arginine (Arg), histidine (His) and lysine (Lys). The method is based on the aggregation of the QC-AuNPs that is caused by these amino acids and leads to a visually detectable color change from red to blue. The absorption maxima shift from 525 nm to 702, 693, and 745 nm, respectively. Aggregations are confirmed by dynamic light scattering (DLS) and transmission electron microscopic techniques (TEM). The effects of the QC concentration, temperature and reaction time for the preparation of QC-Au NPs were tested. Other amino acids do not interfere. Under the optimal conditions, linear relationships exist between the absorption ratios at 702/525 nm (for Arg), 693/525 nm (for His), and 745/525 nm (for Lys) over the concentrations ranges from 2.5–1,250 μM (Arg) and 1–1,000 μM (His and Lys), respectively. The respective limits of detection are 0.04, 0.03, and 0.02 μM. The method provides a useful tool for the rapid visual and instrumental determination of the three amino acids.
We report the use of quercetin as novel reagent for preparation and functionalization of gold nanoparticles to colorimetric sensing of three aminoacids (arginine, histidine and lysine). This is based on the aggregation of QC-AuNPs induced by three aminoacids.
A label-free and single-step method is reported for rapid and highly sensitive detection of bisphenol A (BPA) in aqueous samples. It utilizes an aptamer acting as a probe molecule immobilized on a commercially available array of interdigitated aluminum microelectrodes. BPA was quantified by measuring the interfacial capacitance change rate caused by the specific binding between bisphenol A and the immobilized aptamer. The AC signal also induces an AC electrokinetic effect to generate microfluidic motion for enhanced binding. The capacitive aptasensor achieves a limit of detection as low as 10 fM(2.8 fg ⋅ mL − 1) with a 20 s response time. The method is inexpensive, highly sensitive, rapid and therefore provides a promising technology for on-site detection of BPA in food and water samples.
A. AC electrokinetics effect plays a vital role in BPA detection by introducing microfluidic movement to accelerate the molecular transport to the electrode surface.
B. The ACEK capacitive aptasensor has a limit of detection as low as 10 fM (2.8 fg ⋅ mL − 1) with a 20-s response time.