An electrochemiluminescent (ECL) aptamer based method is described for the determination of thrombin. Three-dimensional nitrogen-doped graphene oxide (3D-NGO) was placed on a glassy carbon electrode (GCE) to provide an electrode surface that displays excellent electrical conductivity and acts as a strong emitter of ECL. The modified electrode was further coated with chitosan via electrodeposition. Finally, the amino-modified aptamer was immobilized on the modified GCE. The interaction between thrombin and aptamer results in a decrease in ECL. The assay has a linear response in the 1 fM to 1 nM thrombin concentration range and a 0.25 fM lower detection limit (at an S/N ratio of 3). The method was applied to the determination of thrombin in spiked human plasma samples, and recoveries ranged between 94 and 105% (with RSDs of <3.6%). The calibration plot was recorded at potential and wavelength of fluorescence emission (wavelength:?445 nm; potential:?0 to -2 V).
Graphical abstract A bare glassy carbon electrode (GCE) does not display electrochemiluminescence (ECL). If, however, nitrogen-doped graphene quantum dots, chitosan, and three-dimensional nitrogen-doped graphene oxide (NGQD-chitosan/3D-NGO) are electrodeposited on the GCE, strong ECL can be observed. The ECL intensity decreased after aptamer and bovine serum albumin (BSA) were dropped onto the electrode (curve a). However, the ECL further decreases after addition of thrombin (TB; curve b).
A voltammetric sensor is described for the determination the antibiotic sulfamethoxazole (SMZ). It is based on the use of a glassy carbon electrode (GCE) modified with a nanocomposite prepared from graphitic carbon nitride and zinc oxide (g-C3N4/ZnO). The nanorod-like ZnO nanostructure were synthesized sonochemically. The g-C3N4/ZnO nanocomposite was then prepared by mixing g-C3N4 with ZnO, followed by ultrasonication. The morphology and structure of the nanocomposite were characterized by X-ray diffraction, Fourier-transform infrared spectroscopy and transmission electron microscopy. Under the optimal conditions, the response of the electrode, typically measured between 0.8 and 0.9 V (vs. Ag/AgCl), increases linearly in the 20 nM to 1.1 mM SMZ concentration range, and the lower detection limit is 6.6 nM. This is better than that of many previously reported sensors for SMZ. The modified electrode is highly selective, well reproducible and maintains its activity for at least 4 weeks. It was applied to the determination of SMZ in spiked human blood serum samples in with satisfactory results.
Graphical abstract Schematic presentation of the voltammetric sensor for sulfamethoxazole. It consists of a glassy carbon electrode modified with a nanocomposite prepared from graphitic carbon nitride (g-C3N4/ZnO) that was supported with zinc oxide nanorods.
A glassy carbon electrode (GCE) modified with polymeric nanocomposite consisting of palladium nanoparticles and a conductive polymeric ionic liquid was prepared. The modified GCE was applied to sensitive and fairly selective electrochemical determination of the mycotoxin zearalenone. Electrocatalytic oxidation is performed in a solution containing 20 % (V/V) acetonitrile and 80 % (V/V) of 1 M perchloric acid. Cyclic voltammetry and square wave voltammetry revealed a well-defined electrocatalytic peak current at overpotential of +0.69 V versus Ag/AgCl. Under optimized experimental conditions, there is a linear relationship between anodic peak current and zearalenone concentration in the range from 0.03 to 35 ng?mL￣1, and the detection limit is 0.01 ng?mL￣1. The method was successfully applied to the analysis of zearalenone in spiked food samples and gave recoveries between 95.6 and 104.0 %.
Graphical abstract The nanocomposite (PdVC-PIL) was prepared by polymerization of ionic liquid monomer (PIL) in presence of Pd nanoparticles on Vulcan XC-72R carbon (PdVC). The solution containing nanocomposite was placed on the glassy carbon electrode (GCE). The voltammetry activity of modified electrode (PdVC-PIL/GCE) was compared to a bare GCE for zearalenone determination.
A nanocomposite modified with dibenzo-18-crown-6 was synthesized and applied as a new sorbent for the preconcentration of thallium(I) via ultrasound assisted-solid phase extraction. This extraction step was combined with electrothermal atomic absorption spectrometry to determine ultra-trace amounts of thallium(I). The nanocomposite was characterized by Fourier transform infrared spectroscopy, X-ray diffraction spectrometry, field emission scanning electron microscopy and transmission electron microscopy. Under the optimized conditions, a dynamic linear range from 7.0 to 435 ng L?1, a detection limit of 1.8 ng L?1 and a quantification limit of 6.0 ng L?1 were obtained. Also, the intra- and inter-day relative standard deviations for 20.0 ng mL?1 Tl(I) were calculated as ±4.8% and ±5.1%, respectively. The adsorbent was applied to the determination of thallium(I) in the environmental, biological and standard samples with satisfactory results.
Graphical abstract A magnetic nanocomposite was synthesized as adsorbent from halloysite nanotubes and a crown ether. Tl(I) ions were extracted selectively and determined by electrothermal atomic absorption spectrometry.
A binary nanocomposite of type copper tungstate and polyaniline (CuWO4@PANI) is described that was obtained by single step polymerization on the surface of a glassy carbon electrode (GCE). The resulting electrode is shown to be a viable tool for voltammetric sensing of quercetin (Qn) in blood, urine and certain food samples. The nanocomposite was characterized by UV-visible absorption spectroscopy, Fourier-transform infrared spectroscopy, thermogravimetric analysis, X-ray diffraction and high-resolution transmission electron microscopy. Differential pulse voltammetry was applied to quantify Qn, typically at the relatively low working potential of 0.15 V (vs. Ag/AgCl). The modified GCE has a wide analytical range (0.001–0.500 μM) and a low detection limit (1.2 nM). The sensor is reproducible, selective and stable. This makes it suitable for determination of Qn in real samples without complicated sample pretreatment.
Graphical abstract Schematic of a copper tungstate and polyaniline nanocomposite modified glassy carbon electrode for voltammetric determination of quercetin in real samples.
Three-dimensional structures comprising polypyrrole nanowires (PPyNWs) and molecularly imprinted polymer (MIP) were prepared by electropolymerization on the surfaces of a glassy carbon electrode (GCE). The modified GCE possesses both large surface area and good electrocatalytic activity for oxidizing dopamine (DA), and this leads to high sensitivity. The electropolymerized MIP has a large number of accessible surface imprints, and this makes the GCE more selective. Under optimal conditions and at a working voltage of typically 0.23 V (vs. SCE), the calibration plot is linear in the 50 nM to 100 μM DA concentration range, and the limit of detection is 33 nM. The sensor has been successfully applied to the analysis of DA in injections.
Graphical abstract Schematic of a three-dimensional nanocomposite based dopamine sensing platform based on the use of a molecularly imprinted polymer and poly(pyrrole) nanowires. The modified polypyrrole nanowires and molecularly imprinted polymer endowed high electrocatalytic capacity and good selectivity for dopamine recognition, respectively.
A glassy carbon electrode (GCE) was modified with poly(L-arginine) (P-Arg), reduced graphene oxide (rGO) and gold nanoparticle (AuNP) to obtain an electrode for simultaneous determination of dopamine (DA), serotonin (5-HT) and L-tryptophan (L-Trp) in the presence of ascorbic acid (AA). The modified GCE was prepared via subsequent ‘layer-by-layer’ deposition using an electrochemical technique. The surface morphology of the modified electrode was studied by scanning electron microscopy, and electrochemical characterizations were carried out via cyclic voltammetry and electrochemical impedance spectroscopy. The modified electrode showed excellent electrocatalytic activity toward DA, 5-HT and L-Trp at pH 7.0. Figures of merit for the differential pulse voltammetric reponse are as follows: (a) Response to DA is linear in two intervals, viz. 1.0–50 nM and 1.0–50 μM DA concentration range, the typical working voltage is 202 mV (vs. Ag/AgCl), and the detection limit is 1 nM (at an S/N ratio of 3). For 5-HT, the respective data are 10 to 500 nM and 1.0 to 10 μM, 381 mV, and 30 nM. For L-Trp, the respective data are 10–70 nM and 10–100 μM, 719 mV, and 0.1 μM. The modified GCE is fairly selective. It was successfully applied to the simultaneous determination of DA, 5-HT, and L-Trp in spiked urine samples, and high recovery rates were found.
Graphical abstract Schematic presentation of the voltammetric sensor based on a glassy carbon electrode modified with poly(L-arginine), reduced graphene oxide (rGO) and gold nanoparticle (GCE/P-Arg/ErGO/AuNP) for simultaneous determination of dopamine (DA), serotonin (5-HT) and L-tryptophan (L-Trp).
Nanodiamonds were modified such that they carry thiol groups (ND-thiol). Gold nanoparticles were reacted with ND-thiol to obtain a highly stable conjugate of the type ND@AuNPs. Both ND-thiol and the ND@AuNPs were characterized by SEM, TEM, AFM, DLS, zeta potential, XPS, XRD, UV-Vis, Raman, FTIR and cytotoxicity studies. Their biocompatibility was confirmed via an MTT assay with HeLa cells. At a pH value of 6, the ND@AuNPs represent a colorimetric probe that can be used to selectively detect the illegally used β-adrenergic drug clenbuterol (CLB) and the pollutant chromium(III). Detection can be performed visually by monitoring the color change from wine red to purple blue, or by colorimetric measurement of the so-called SPR peaks at 651 and 710 nm. The color changes are due to aggregation, and this is confirmed by TEM and DLS data. The involvement of surface functional groups that assist in analyte recognition was verified by FTIR. The detection limits are 0.49 nM for CLB, and 0.37 nM for Cr(III). The ND@AuNPs were successfully applied to the determination of Cr(III) and CLB in spiked human urine samples. Notably, the low interference by other ions in the detection of Cr(III) in tap and lake water is confirmed by ICP-MS analyses.
Graphical abstract Nanodiamonds carrying thiol groups (ND-Thiol) were conjugated to gold nanoparticles, and the resulting ND@AuNPs are shown to be viable probes for the colorimetric detection of sub-nanomolar levels of clenbuterol (CLB) and Cr(III) ions, with demonstrated applicability to real water and urine samples.
The authors describe a dye-sensitized photoelectrochemical immunoassay for the tumor marker carcinoembryonic antigen (CEA). The method employs the rhodamine dye Rh123 with red color and absorption maximum at 500 nm for spectral sensitization, and a 3D nanocomposite prepared from graphene oxide and MoS2 acting as the photoelectric conversion layer. The nanocomposite with flower-like 3D architectures was characterized by transmission electron microscopy, scanning electron microscopy, X-ray powder diffraction, and UV-vis diffuse reflectometry. A photoelectrochemical sandwich immunoassay was developed that is based on the use of the nanocomposite and based on the specific binding of antibody and antigen, and by using a secondary antibody labeled with Rh123 and CdS (Ab2-Rh123@CdS). Under optimal conditions and at a typical working voltage of 0 V (vs. Hg/HgCl2), the photocurrent increases linearly 10 pg mL?1 to 80 ng mL?1 CEA concentration range, with a 3.2 pg mL?1 detection limit.
Graphical abstract Flower-like GO-MoS2 complex with high efficiency of electron transport was synthesized to construct photoelectrochemical platform. The sandwich-type immunoassay was built on this platform based on specific binding of antigen and antibody. Carcinoembryonic antigen in sample was detected sensitively by using sensitization of rhodamine dye Rh123 as signal amplification strategy.
A glassy carbon electrode (GCE) was modified with a nanocomposite consisting of tetraoctylammonium bromide (TOAB), C60 fullerene, and palladium nanorods (PdNRs). The PdNRs were hydrothermally prepared and had a typical width of 20 ± 2 nm. The nanocomposite forms stable films on the GCE and exhibits a reversible redox pair for the C60/C60? system while rendering the surface to be positively charged. The modified GCE was applied to fabricate an electrochemical biosensor for detecting acetylcholinesterase (AChE) by measurement of the amount of thiocholine formed from acetylthiocholine, best at a working voltage of ?0.19 V (vs. SCE). The detection scheme is based on (a) measurement of the activity of ethyl paraoxon-inhibited AChE, and (b) measurement of AChE activity after reactivation with pralidoxime (2-PAM). Compared to the conventional methods using acetylthiocholine as a substrate, the dual method presented here provides data on the AChE activity after inhibition and subsequent reactivation, thereby yielding credible data on reactivated enzyme activity. The linear analytical range for AChE activity extends from 2.5 U L?1 to 250 kU·L?1, and the detection limit is 0.83 U L?1.
Graphical abstract Cyclovoltammetric acetylcholinesterase (AChE) activity assay is constructed based on the palladium nanorods composited with functionalized C60 fullerene (PdNR/C60 + TOAB), which aims to measure the signal change between ethyl paraoxon-inhibited and subsequent pralidoxime (2-PAM)-reactivated AChE activity.
A nanocomposite consisting of cetyltrimethylammonium bromide (CTAB), Fe3O4 nanoparticles and reduced graphene oxide (CTAB-Fe3O4-rGO) was prepared, characterized, and used to modify the surface of a glassy carbon electrode (GCE). The voltammetric response of the modified GCE to 4-nonylphenol (NPh) was investigated by cyclic voltammetry and revealed a strong peak at around 0.57 V (vs. SCE). Under optimum conditions, the calibration plot is linear in the ranges from 0.03 to 7.0 μM and from 7.0 to 15.0 μM, with a 8 nM detection limit which is lower that that of many other methods. The modified electrode has excellent fabrication reproducibility and was applied to the determination of NPh in spiked real water samples to give recoveries (at a spiking level of 1 μM) between 102.1 and 99.1%.
Graphical abstract A nanocomposite consisting of cetyltrimethylammonium bromide (CTAB), Fe3O4 nanoparticles and reduced graphene oxide (CTAB-Fe3O4-rGO) was prepared and used to modify the surface of a glassy carbon electrode (GCE) for the differential pulse voltammetric (DPV) determination of 4-nonylphenol (NPh).
The authors demonstrate the exploitation of reduced graphene oxide (RGO) as a template for immobilizing zeolitic imidazolate framework-8 (ZIF-8) crystals loaded with the electrochemical probe Methylene Blue (MB). The framework was deposited on the surface of RGO in a one-pot process. Transmission electron microscopy, scanning electron microscopy and X-ray diffraction were employed to characterize the nanocomposite. The electrochemical behavior of rutin at a glassy carbon electrode (GCE) modified with the nanocomposite was investigated by cyclic voltammetry and differential pulse voltammetry. The modified GCE displays high electrocatalytic activity toward rutin oxidation at a relatively low working potential (0.4 V vs. Ag/AgCl). Under the optimal conditions, the sensor has an amperometric response that is linear in the 0.1 to 100 μM rutin concentration range, with a 20 nM detection limit (at an S/N ratio of 3). The method was successfully applied to the determination of rutin in tablets and urine samples.
Graphical abstract The zeolitic imidazolate framework ZIF-8 was loaded with Methylene Blue and deposited on the surface of reduced graphene oxide. A glassy carbon electrode was modified with the nanocomposite and then used for the determination of rutin with a 20 nM detection limit and a linear range from 0.1 to 100 μM.
A nanocomposite consisting of polyaniline and multiwalled carbon nanotubes was tethered with a thiolated thrombin-specific aptamer and placed on a glassy carbon electrode (GCE) to obtain a biosensor for thrombin that has a limit of detection of 80 fM. Tethering was accomplished via a thiol-ene reaction between thiolated thrombin aptamer (TTA) and oxidized polyaniline (PANI) that was chemically synthesized in the presence of solution-dispersed multiwalled carbon nanotubes (MWCNTs). The modified GCE exhibits a pair of well-defined redox peaks (at 50/?25 mV) of self-doped PANI in neutral solution, and the tethered TTA-thrombin interaction gives a decreased electrochemical signal. Cyclic voltammetry, scanning electron microscopy and ultraviolet visible spectroscopy were used to characterize the film properties. This amperometric aptasensor is sensitive, selective and reproducible. It was applied to the determination of thrombin in spiked human serum (0.2 to 4 nM) and gave recoveries that ranged from 95 to 102%.
Graphical abstract A nanocomposite consisting of polyaniline (PANI) and multiwalled carbon nanotubes (MWCNTs) was tethered with a thiolated thrombin aptamer (TTA) and placed on a glassy carbon electrode (GCE) to obtain a biosensor for thrombin that has a 80 f. detection limit.
An electrochemical chiral multilayer nanocomposite was prepared by modifying a glassy carbon electrode (GCE) via opposite-charge adsorption of amino-modified β-cyclodextrin (NH2-β-CD), gold-platinum core-shell microspheres (Au@Pts), polyethyleneimine (PEI), and multi-walled carbon nanotubes (MWCNTs). The modified GCE was applied to the enantioselective voltammetric determination of tryprophan (Trp). The Au@Pts enable an effective immobilization of the chiral selector (NH2-β-CD) and enhance the electrochemical performance. Scanning electron microscopy, transmission electron microscopy, UV-vis spectroscopy, FTIR and electrochemical methods were used to characterize the nanocomposite. Trp enantiomers were then determined by differential pulse voltammetry (DPV) (with a peak potential of +0.7 V vs. Ag/AgCl). The recognition efficiency was expressed by an increase in peak height by about 32% for DPV determinations of L-Trp compared to D-Trp in case of a 5 mM Trp solution of pH 7.0. Response was linear in the 10 μM to 5.0 mM concentration range, and the limits of detection were 4.3 μM and 5.6 μM with electrochemical sensitivity of 43.5 μA·μM?1·cm?2 and 34.6 μA·μM?1·cm?2 for L-Trp and D-Trp, respectively (at S/N =?3).
Graphical Abstract Schematic of an electrochemical chiral multilayer nanocomposite composed of multi-walled carbon nanotubes (MWCNTs), polyethyleneimine (PEI), gold-platinum core-shell microspheres (Au@Pt) and amino-modified β-cyclodextrin (NH2-β-CD). It was prepared by modifying a glassy carbon electrode (GCE) for enantioselective voltammetric determination of tryptophan (Trp) enantiomers.
We describe a chemical exfoliation method for the preparation of MoS2 nanosheets. The nanosheets were incorporated into poly(3,4-ethylenedioxythiophene) (PEDOT) by electrodeposition on a glassy carbon electrode (GCE) to form a nanocomposite. The modified GCE is shown to enable simultaneous determination of ascorbic acid (AA), dopamine (DA) and uric acid (UA). Due to the synergistic effect of MoS2 and PEDOT, this electrode displays better properties in terms of electrocatalytic oxidation of AA, DA and UA than pure PEDOT, which is illustrated by cyclic voltammetry and differential pulse voltammetry (DPV). Under optimum conditions and at pH 7.4, the respective sensitivities and best working potentials are as follows: AA: 1.20 A?mM?1?m?2, 30 mV; DA: 36.40 A?mM?1?m?2, 210 mV; UA: 105.17 A?mM?1?m?2, 350 mV. The calculated detection limits for AA, DA and UA are 5.83 μM, 0.52 μM and 0.95 μM, respectively. The modified electrode was applied to the detection of the three species in human urine samples and gave satisfactory results.
Graphical abstract MoS2 nanosheets were prepared by a facile chemical exfoliation method. MoS2 and poly(3,4-ethylenedioxythiophene) nanocomposite modified glassy carbon electrodes were fabricated, which are shown to enable simultaneous determination of ascorbic acid, dopamine and uric acid with high sensitivity and selectivity.
A composite material obtained by ultrasonication of graphene oxide (GO) and multi-walled carbon nanotubes (MWCNTs) was loaded with manganese dioxide (MnO2), poly(diallyldimethylammonium chloride) and gold nanoparticles (AuNPs), and the resulting multilayer hybrid films were deposited on a glassy carbon electrode (GCE). The microstructure, composition and electrochemical behavior of the composite and the modified GCE were characterized by transmission electron microscopy, Raman spectra, energy-dispersive X-ray spectroscopy, electrochemical impedance spectroscopy and cyclic voltammetry. The electrode induces efficient electrocatalytic oxidation of dopamine at a rather low working voltage of 0.22 V (vs. SCE) at neutral pH values. The response is linear in the 0.5 μM to 2.5 mM concentration range, the sensitivity is 233.4 μA·mM￣1·cm￣2, and the detection limit is 0.17 μM at an SNR of 3. The sensor is well reproducible and stable. It displays high selectivity over ascorbic acid, uric acid and glucose even if these are present in comparable concentrations.
Graphical abstract Gold nanoparticles were self-assembled onto the surface of the MnO2 decorated graphene oxide-carbon nanotubes composites with poly(diallyldimethylammonium chloride) (PDDA) as a coupling agent. Further, a sensitive electrochemical sensor of dopamine was developed via immobilizing this nanocomposite on a glassy carbon electrode (GCE).
The authors describe an aptamer based assay for determination of ractopamine (RAC) by using PicoGreen (PG) as a fluorescent probe specific for dsDNA. In the absence of RAC, the aptamer forms a duplex structure with a complementary sequence that results in enhanced PG fluorescence. Upon binding to RAC, the aptamer undergoes a structural switch. This reduces the number of DNA duplexes formed and causes a reduction of fluorescence intensity of PG as measured at excitation/emission wavelengths of 480/520 nm. Under optimized conditions, the dynamic calibration plot covers the 50 pM to 50 μM concentration range, with a 50 pM detection limit. This meets the safety supervision regulations of the European Commission in terms of residue limits of RAC in food. The method displays high selectivity over other β-adrenergic agonists including clenbuterol, dopamine and salbutamol. The assay was successfully applied to samples of swine urine at spiking levels of 7.4 nM, 22.2 nM and 37 nM. Average recoveries ranged from 95 to 110%, with an RSD of <1.5%. The method is expected to represent a promising tool for simple, rapid and sensitive on-site detection of RAC in animal products.
Graphical abstract An aptamer based fluorescent assay for determination of ractopamine was developed with a dynamic range of 50 pM to 50 μM. The average recovery from spiked urine samples ranged from 95 to 110%, with an RSD of <1.5%.
The authors describe a method for signal amplification of label-free voltammetric immunosensors. A glassy carbon electrode (GCE) was modified with Prussian Blue-platinum nanoparticles (PB-PtNPs) as a redox-active species that gives a strong amperometric signal at 0.18 V (vs. Ag/AgCl). Benefitting from the excellent electrical conductivity and the strong catalytic activity to H2O2, the modified GCE gives a strongly enhanced signal. The PB-PtNPs were incorporated into a polyaniline (PANI) hydrogel to further enhance the signal. The signal response of the PB-PtNP-PANI/GCE is larger by a factor of 7.6 than that of PB-PtNP/GCE. In order to further improve electrical conductivity and immobilize antibody, gold nanoparticles (AuNPs) were deposited on the surface of the PB-PtNP-PANI hydrogel. The AuNP-PB-PtNP-PANI hydrogel nanocomposite on the GCE was used in an immunosensor for the model analyte carcinoma antigen 125 (CA125), a biomarker for epithelial ovarian cancer, by immobilizing the respective antibody on the modified GCE. A linear response found for the 0.01 to 5000 U mL?1 CA125 concentration range, with a detection limit of 4.4 mU mL?1 (at an S/N ratio of 3). The electrochemical sensitivity is as high as 119.76 μA·(U/mL)?1·cm?2. The detection of CA125 in human serum showed satisfactory accuracy compared to a commercial chemiluminescent microparticle immunoassay (CMIA).
Graphical abstract Schematic of a nanocomposites consisting of gold nanoparticles, Prussian Blue, platinum nanoparticles and polyaniline hydrogel as a signal multi-amplification sensing substrate for the ultrasensitive immuno detection of carcinoma antigen 125 (CA125).
A highly sensitive electrochemical sensor is described for the determination of H2O2. It is based on based on the use of polyaniline that was generated in-situ and within 1 min on a glassy carbon electrode (GCE) with the aid of the Fe(II)/H2O2 system. Initially, a 2-dimensional composite was prepared from graphene oxide and polyamidoamine dendrimer through covalent interaction. It was employed as a carrier for Fe(II) ions. Then, the nanocomposite was drop-coated onto the surface of the GCE. When exposed to H2O2, the Fe(II) on the GCE is converted to Fe(III), and free hydroxy radicals are formed. The Fe(III) ions and the hydroxy radicals catalyze the oxidation of aniline to produce electroactive polyaniline on the GCE. The resulting sensor, best operated at a working potential as low as 50 mV (vs. SCE) which excludes interference by dissolved oxygen, has a linear response in the 500 nM to 2 mM H2O2 concentration range, and the detection limit is 180 nM. The sensor was successfully applied to the determination of H2O2 in spiked milk and fetal bovine serum samples.
Graphical abstract Schematic presentation of a sensitive electrochemical sensor employed for detection of H2O2 in sophisticated matrices by using graphene oxide-PAMAM dendrimer as initiator container and Fe2+/H2O2 system as signal enhancer.
The family of zearalenones (ZENs) represents a major group of mycotoxins with estrogenic activity. They are produced by Fusarium fungi and cause adverse effects on human health and animal production. The authors describe here a label-free amperometric immunosensor for the direct determination of ZENs. A glassy carbon electrode (GCE) was first modified with polyethyleneimine-functionalized multi-walled carbon nanotubes. Next, gold and platinum nanoparticles (AuPt-NPs) were electro-deposited. This process strongly increased the surface area for capturing a large amount of antibodies and enhanced the electrochemical performance. In a final step, monoclonal antibody against zearalenone was orientedly immobilized on the electrode, this followed by surface blocking with BSA. The resulting biosensor was applied to the voltammetry determination of ZENs, best at a working voltage of 0.18 V (vs SCE). Under optimized conditions, the method displays a wide linear range that extends from 0.005 to 50 ng mL?1, with a limit of detection of 1.5 pg mL?1 (at an S/N ratio of 3). The assay is highly reproducible and selective, and therefore provides a sensitive and convenient tool for determination of such mycotoxins.
Graphical abstract An amperometric immunosensor for the direct determination of ZENs has been developed by immobilizing anti-ZEN monoclonal antibody on multi-walled carbon nanotubest hat were deposited, along with gold and platinum nanoparticles, on a glassy carbon electrode modified with Staphylococcus protein A.
