Highly sensitive electrochemical sensor based on β-cyclodextrin–gold@3, 4, 9, 10-perylene tetracarboxylic acid functionalized single-walled carbon nanohorns for simultaneous determination of myricetin and rutin

The application of macrocyclic hosts for construction of different electrochemical devices and separation matrices has attracted much attentions due to their benign biocompatibility and simplicity of synthesis. Myricetin and rutin are considered two of the most bioactive flavonoids, which have been proved to exhibit various physiological functions. This work reports a simple and facile approach for the synthesis of β-cyclodextrin-gold@3, 4, 9, 10-perylene tetracarboxylic acid functionalized single-walled carbon nanohorns (β-CD–Au@PTCA–SWCNHs) nanohybrids. The simultaneous electrochemical determination of myricetin and rutin using a β-CD–Au@PTCA–SWCNHs-modified glassy carbon electrode was established. The results show that the β-CD–Au@PTCA–SWCNHs-modified electrode displayed electrochemical signal superior to those of Au@PTCA–;SWCNHs and SWCNHs towards myricetin and rutin. The proposed modified electrode has a linear response range of 0.01–10.00 μM both for myricetin and rutin with relatively low detection limits of 0.0038 μM for myricetin and 0.0044 μM (S/N = 3) for rutin, respectively. The excellent performance of the sensing platform is considered to be the synergic effects of the SWCNHs (e.g. their good electrochemical properties and large surface area) and β-CD (e.g. a hydrophilic external surface, a high supramolecular recognition, and a good enrichment capability).     

Enhancement of sensitivity of paper-based sensor array for the identification of heavy-metal ions

Paper-based microfluidic devices have been widely investigated in recent years. Among various detection techniques, colorimetric method plays a very important role in paper-based microfluidic devices. The limitation, however, is also clear: they generally require highly sensitive indicators. In this work, we have developed a novel enrichment-based paper test for the discrimination of heavy-metal ions. Comparing to regular paper-based microfluidic devices, enrichment-based technique showed largely improved sensitivity. Combining with eight pyridylazo compounds and array technologies-based pattern-recognition, we have obtained the discrimination capability of eight different heavy-metal ions at same concentration as low as 50 μM using our enrichment-based pyridylazo compounds array paper. Identification of the heavy-metal ions was readily achieved using a standard chemometric approach. This method can be, of course, used for other analytes as well.     

Sensitive and selective electrochemical detection of artemisinin based on its reaction with p-aminophenylboronic acid

The electrochemical detection of artemisinin generally requires high oxidation potential or the use of complex electrode modification. We find that artemisinin can react with p-aminophenylboronic acid to produce easily electrochemically detectable aminophenol for the first time. By making use of the new reaction, we report an alternative method to detect artemisinin through the determination of p-aminophenol. The calibration curve for the determination of artemisinin is linear in the range of 2 μmol L⁻¹ to 200 μmol L⁻¹ with the detection limit of 0.8 μmol L⁻¹, which is more sensitive than other reported electrochemical methods. The relative standard deviation is 4.83% for the determination of 10 μM artemisinin. Because the oxidation potential of p-aminophenol is around 0 V, the present method is high selective. When 40 μM, 90 μM and 140 μM of artemisinin were spiked to compound naphthoquine phosphate tablet samples, the recoveries are 107.6%, 105.4% and 101.7%, respectively. This detection strategy is attractive for the detection of artemisinin and its derivatives. The finding that artemisinin can react with aromatic boronic acid has the potential to be exploited for the development of other sensors, such as fluorescence artemisinin sensors.     

Facile hydrothermal growth graphene/ZnO nanocomposite for development of enhanced biosensor

Graphene/zinc oxide nanocomposite was synthesised via a facile, green and efficient approach consisted of novel liquid phase exfoliation and solvothermal growth for sensing application. Highly pristine graphene was synthesised through mild sonication treatment of graphite in a mixture of ethanol and water at an optimum ratio. The X-ray diffractometry (XRD) affirmed the hydrothermal growth of pure zinc oxide nanoparticles from zinc nitrate hexahydrate precursor. The as-prepared graphene/zinc oxide (G/ZnO) nanocomposite was characterised comprehensively to evaluate its morphology, crystallinity, composition and purity. All results clearly indicate that zinc oxide particles were homogenously distributed on graphene sheets, without any severe aggregation. The electrochemical performance of graphene/zinc oxide nanocomposite-modified screen-printed carbon electrode (SPCE) was evaluated using cyclic voltammetry (CV) and amperometry analysis. The resulting electrode exhibited excellent electrocatalytic activity towards the reduction of hydrogen peroxide (H₂O₂) in a linear range of 1–15 mM with a correlation coefficient of 0.9977. The sensitivity of the graphene/zinc oxide nanocomposite-modified hydrogen peroxide sensor was 3.2580 μAmM⁻¹ with a limit of detection of 7.4357 μM. An electrochemical DNA sensor platform was then fabricated for the detection of Avian Influenza H5 gene based on graphene/zinc oxide nanocomposite. The results obtained from amperometry study indicate that the graphene/zinc oxide nanocomposite-enhanced electrochemical DNA biosensor is significantly more sensitive (P < 0.05) and efficient than the conventional agarose gel electrophoresis.     

Exploiting multi-function Metal-Organic Framework nanocomposite Ag@Zn-TSA as highly efficient immobilization matrixes for sensitive electrochemical biosensing

A novel multi-function Metal-Organic Framework composite Ag@Zn-TSA (zinc thiosalicylate, Zn(C₇H₄O₂S), Zn-TSA) was synthesized as highly efficient immobilization matrixes of myoglobin (Mb)/glucose oxidase (GOx) for electrochemical biosensing. The electrochemical biosensors based on Ag@Zn-TSA composite and ionic liquid (IL) modified carbon paste electrode (CPE) were fabricated successfully. Furthermore, the properties of the sensors were discussed by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and amperometric current-time curve, respectively. The results showed the proposed biosensors had wide linear response to hydrogen peroxide (H₂O₂) in the range of 0.3–20,000 μM, to nitrite (NO₂⁻) for 1.3 μM–1660 μM and 2262 μM–1,33,000 μM, to glucose for 2.0–1022 μM, with a low detection limit of 0.08 μM for H₂O₂, 0.5 μM for NO₂⁻, 0.8 μM for glucose. The values of the apparent heterogeneous electron transfer rate constant (k_s) for Mb and GOx were estimated as 2.05 s⁻¹ and 2.45 s⁻¹, respectively. Thus, Ag@Zn-TSA was a kind of ideal material as highly efficient immobilization matrixes for sensitive electrochemical biosensing. In addition, this work indicated that MOF nanocomposite had a great potential for constructing wide range of sensing interface.     

Coupling of a Reagentless Electrochemical DNA Biosensor with Conducting Polymer Film and Nanocomposite as Matrices for the Detection of the HIV DNA Sequences

Abstract

This paper describes a reagentless electrochemical DNA biosensor applied to the detection of human immunodeficiency virus (HIV) sequences based on electrochemical impedance spectroscopy (EIS). The novel DNA biosensor has been elaborated by means of an opposite‐charged adsorption Au‐Ag nanocomposite to a conductive polymer polypyrrole (PPy) modified platinum electrode (Pt) and self‐assembly the mercapto oligonucleotide probes onto the surface of modified electrode via the nanocomposite. The duplex formation was detected by measuring the electrochemical impedance signal of nucleic acids in phosphate buffer solution (PBS). Such response is based on the concomitant conductivity changes of the PPy film and nanocomposite. The reagentless scheme has been characterised using 21‐mer synthetic oligonucleotides as models: parameters affecting the hybridization assay were explored and optimized. The detection limit is 5.0×10^?10 M of target oligonucleotides at 3σ. The potential for development of reagentless DNA hybridization analysis in the clinical diagnosis is being pursued.     

Highly selective and sensitive simple sensor based on electrochemically treated nano polypyrrole-sodium dodecyl sulphate film for the detection of para-nitrophenol

An ultrasensitive and highly selective electrochemical sensor for the determination of p-nitrophenol (p-NP) was developed based on electrochemically treated nano polypyrrole/sodium dodecyl sulphate film (ENPPy/SDS film) modified glassy carbon electrode. The nano polypyrrole/sodium dodecyl sulphate film (NPPy/SDS film) was prepared and treated electrochemically in phosphate buffer solution. The surface morphology and elemental analysis of treated and untreated NPPy/SDS film were characterized by FESEM and EDX analysis, respectively. Wettability of polymer films were analysed by contact angle test. The hydrophilic nature of the polymer film decreased after electrochemical treatment. Effect of the pH of electrolyte and thickness of the ENPPy/SDS film on determination of p-NP was optimised by cyclic voltammetry. Under the optimised conditions, the p-NP was determined from the oxidation peak of p-hydroxyaminophenol which was formed from the reduction of p-NP in the reduction segment of cyclic voltammetry. A very good linear detection range (from 0.1 nM to 100 μM) and the best LOD (0.1 nM) were obtained for p-NP with very good selectivity. This detection limit is below to the allowed limit in drinking water, 0.43 μM, proposed by the U.S. Environmental Protection Agency (EPA) and earlier reports. Moreover, ENPPy/SDS film based sensor exhibits high sensitivity (4.4546 μA μM⁻¹) to p-NP. Experimental results show that it is a fast and simple sensor for p-NP.     

Single-walled carbon nanotube-arrayed microelectrode chip for electrochemical analysis

The development of a single-walled carbon nanotube (SWCNT)-arrayed microelectrode chip is reported here. SWCNT-arrayed electrodes were formed directly on Pt surfaces, and were also arrayed on the chip. The electrochemical characteristics of the devices were investigated using potassium ferricyanide, K₃[Fe(CN)₆] in connection with cyclic voltammetry (CV). The electrochemical signals of electro-active amino acids; L-Tyrosine (Tyr), L-Cysteine (Cys) and L-Tryptophan (Trp) were detected using differential pulse voltammetry (DPV). The chip operated at a lower oxidation potential (vs. Ag/AgCl) compared with conventional carbon and Pt disc electrodes in 50 mM phosphate buffer solution (PBS, pH 7.4). The linear response was observed between 0.1–1 μM and 100 μM for the amino acids with correlation coefficients higher than 0.99. The electrochemical measurements of K₃[Fe(CN)₆] and amino acids revealed that the peak current intensities using SWCNT-arrayed electrodes were about 100-fold higher than those using bare Pt-arrayed microelectrodes. Additionally, the surface area dependence of the peak current responses was plotted. We concluded that our chips with SWCNT-arrayed microelectrodes provided a promising platform for electrochemical applications.     

Electrospun Pd nanoparticles loaded on Vulcan carbon/ conductive polymeric ionic liquid nanofibers for selective and sensitive determination of tramadol

In the present work a sensitive and selective electrochemical sensor was fabricated based on a glassy carbon electrode which has been modified with Pd nanoparticles loaded on Vulcan carbon/conductive polymeric ionic liquid composite nanofibers. The nanostructures were characterized by UV–Vis, FT-IR, FESEM, EDX and XRD techniques. The electrochemical study of the modified electrode, as well as its efficiency for the electrooxidation of tramadol was described in 0.1 M phosphate buffered solution (PBS) (pH 7.0) using cyclic voltammetry, linear sweep voltammetry, chronoamperometry and square wave voltammetry as diagnostic techniques. It has been found that application of the composite nanofibers result in a sensitivity enhancement and a considerable decrease in the anodic overpotential, leading to negative shifts about 200 mV in peak potential. The results exhibit a linear dynamic range from 0.05 μM to 200 μM and a detection limit of 0.015 μM for tramadol. Finally, the modified electrode was used for the determination of tramadol in pharmaceutical and biological samples.     

Synthesis of a novel electrode material containing phytic acid-polyaniline nanofibers for simultaneous determination of cadmium and lead ions

The development of nanostructured conducting polymers based materials for electrochemical applications has attracted intense attention due to their environmental stability, unique reversible redox properties, abundant electron active sites, rapid electron transfer and tunable conductivity. Here, a phytic acid doped polyaniline nanofibers based nanocomposite was synthesized using a simple and green method, the properties of the resulting nanomaterial was characterized by electrochemical impedance spectroscopy (EIS), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). A glassy carbon electrode modified by the nanocomposite was evaluated as a new platform for the simultaneous detection of trace amounts of Cd²⁺ and Pb²⁺ using differential pulse anodic stripping voltammetry (DPASV). The synergistic contribution from PANI nanofibers and phytic acid enhances the accumulation efficiency and the charge transfer rate of metal ions during the DPASV analysis. Under the optimal conditions, good linear relationships were obtained for Cd²⁺ in a range of 0.05–60 μg L⁻¹, with the detection limit (S/N = 3) of 0.02 μg L⁻¹, and for Pb²⁺ in a range of 0.1–60 μg L⁻¹, with the detection limit (S/N = 3) of 0.05 μg L⁻¹. The new electrode was successfully applied to real water samples for simultaneous detection of Cd²⁺ and Pb²⁺ with good recovery rates. Therefore, the new electrode material may be a capable candidate for the detection of trace levels of heavy metal ions.     

Development of an ionic liquid modified screen-printed graphite electrode and its sensing in determination of dopamine

A novel screen-printing ink consisted of graphite, cellulose acetate and ionic liquid n-octylpyridinum hexafluorophosphate (OPPF) was developed and investigated. The graphite–cellulose acetate system was employed as the basic ink system, which could be easily printed onto the ploy(vinyl chloride) (PVC) substrate. With the natural viscosity and high conductivity of OPPF, the screen-printed electrode (SPE) from the OPPF modified ink exhibited very attractive properties, such as high stability and electrochemical reactivity, low background current and wide electrochemical window. Furthermore, the electrode possessed excellent electrocatalytic activity for the oxidation of dopamine. The linear range for the determination of dopamine was from 1.0 μM to 2.5 mM and the detection limit was 0.5 μM.     

Design of novel,simple, and inexpensive 3D printing-based miniaturized electrochemical platform containing embedded disposable detector for analytical applications

This paper describes the development of a novel, simple, and inexpensive electrochemical device containing an integrated and disposable three-electrode system for detection. The base of this platform consists on a PDMS structure containing microchannels which were prototyped using 3D-printed molds. Pencil graphite leads were inserted into these microchannels and utilized as working, counter and reference electrodes in a novel design. Morphological analysis and electrochemical experiments with benchmark redox probes were carried out in order to evaluate the performance and characterize the miniaturized device proposed. Even using inexpensive materials and a simple fabrication protocol, the electrochemical platform developed provided good repeatability and reproducibility over a low cost (ca. $2 per device), acceptable lifetime (ca. 250 voltammetric runs) and extremely reduced consumption of samples and reagents (order of µL). As proof of concept, the analytical feasibility of the platform was investigated through the simultaneous determination of dopamine (DOPA) and acetaminophen (AC). The two analytes showed linear dependence on the concentration range from 1 to 15 µM and the LODs achieved were 0.21 µM for DOPA and 0.29 µM for AC. Moreover, the platform was successfully applied on the determination of DOPA and AC in spiked blood serum and urine samples. The results obtained with the device described here were better than some reports in literature that use more costly electrodic materials and complex modification steps for the detection of the same analytes.     

Construction of zinc selenide microspheres decorated with octadecylamine-functionalized reduced graphene oxide as an effective catalyst for the dual-mode detection of chloroquine phosphate

Zinc selenide microspheres were constructed using a simple hydrothermal technique at 180°C. It was ultrasonically treated with reduced graphene oxide modified with octadecylamine alkyl amine to form a hybrid nanocomposite. The optical, structural, and functional analysis by ultraviolet (UV) absorbance, X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy revealed the crystal nature of the microspheres and the successful formation of the nanocomposite. Field emission scanning electron microscopy and transmission electron microscopy were done to study the morphological properties of the material. It was further used to fabricate a dual-modality sensor using both electrochemical and absorbance techniques for the detection of antimalarial drug chloroquine phosphate (CQP), which was used for the treatment of COVID-19 (SARS-CoV-2) virus. For electrochemical detection, the sensor showed a very low detection limit of 1.43 nM at a linear working range of 0.199–250.06 μM and a high sensitivity of 43.912 μA/μM/cm². For UV-based detection, the sensor showed a very low detection limit of 6.88 nM at a linear working range of 0.045–7.324 μM. The sensor showed excellent analyte recovery rate for real-time analysis in biological as well as environmental samples. The results suggested that the sensor is effective for the detection of CQP with feasibility for future commercialization.     

Direct spectroelectrochemistry of peroxidases immobilised on mesoporous metal oxide electrodes: Towards reagentless hydrogen peroxide sensing

In this paper, we employ two peroxidases (horseradish peroxidase, HRP and cytochrome c peroxidase, CcP) to demonstrate their ability to retain their redox and biological functions after their immobilisation on mesoporous TiO₂ and SnO₂ electrodes. We will also demonstrate the use of HRP immobilised on the metal oxide electrodes for the development of reagentless optical and electrochemical biosensors for the detection of hydrogen peroxide (H₂O₂) with low detection limit of 0.04 and 1 μM, respectively.     

Paper-based scanometric assay for lead ion detection using DNAzyme

A facile and simple paper-based scanometric assay was developed to detect Pb²⁺ using GR5-DNAzyme. Magnetic beads (MBs) and gold nanoparticles (AuNPs) were used as a signal collector and a signal indicator, respectively. They were linked together by GR5-DNAzyme, comprising an enzyme and a substrate strand pairing up with each other. In the presence of Pb²⁺, the substrate strand is cut into two pieces, resulting in the disassembly of AuNPs from the MBs. These AuNPs were spotted on predefined areas on a chromatography paper, where signal is amplified through silver reduction. This sensing platform exhibits high sensitivity and selectivity toward Pb²⁺, giving a detection limit of 0.3 nM and a linear fitting range from 0.1 to 1000 nM. Testing of this biosensor in river water and synthetic urine samples also showed satisfying results. Besides offering simultaneous and multi-sample analysis, this paper-based sensing platform presented here could be potentially applied and served as a general platform for on-site, naked eyes, and low-cost monitoring of other heavy metal ions in environmental and body fluid samples.     

A Novel Superoxide Anion Biosensor for Monitoring Reactive Species of Oxygen Released by Cancer Cells

In this study, novel sensitive and selective hydrogel microstructures to detect superoxide anions released by cancer cells, based on electrochemical biosensors, are proposed. Ferrocene was coupled with superoxide dismutase within a poly(ethylene glycol) diacrylate hydrogel matrix. The pre‐polymer solution was patterned by photolithography in gold microelectrodes fabricated on top of glass slides. The biosensor was characterized by electrochemical impedance spectroscopy and cyclic voltammetry, and was able to detect superoxide anions in a wide linear range from 5 to 100 μM, with a low detection limit of 0.001 μM and sensitivity of 14.1 nA μM/mm². Moreover, the biosensor was able to directly detect reactive oxygen species released from prostate cells. Furthermore, the reproducibility, stability and selectivity of the biosensor achieved better results when compared with the previous report, so this methodology can be used in physiological and pathological detection of reactive oxygen species, providing a powerful platform for clinical diagnostics in the future.     

Total phenol analysis of weakly supported water using a laccase-based microband biosensor

The monitoring of phenolic compounds in wastewaters in a simple manner is of great importance for environmental control. Here, a novel screen printed laccase-based microband array for in situ, total phenol estimation in wastewaters and for water quality monitoring without additional sample pre-treatment is presented. Numerical simulations using the finite element method were utilized for the characterization of micro-scale graphite electrodes. Anodization followed by covalent modification was used for the electrode functionalization with laccase. The functionalization efficiency and the electrochemical performance in direct and catechol-mediated oxygen reduction were studied at the microband laccase electrodes and compared with macro-scale electrode structures. The reduction of the dimensions of the enzyme biosensor, when used under optimized conditions, led to a significant improvement in its analytical characteristics. The elaborated microsensor showed fast responses towards catechol additions to tap water – a weakly supported medium – characterized by a linear range from 0.2 to 10 μM, a sensitivity of 1.35 ± 0.4 A M⁻¹ cm⁻² and a dynamic range up to 43 μM. This enhanced laccase-based microsensor was used for water quality monitoring and its performance for total phenol analysis of wastewater samples from different stages of the cleaning process was compared to a standard method.     

Electrophoretically deposited L-cysteine functionalized MoS2@MWCNT nanocomposite platform: a smart approach toward highly sensitive and label-free detection of gentamicin

The exploitation of antibiotics has caused many side effects on the agriculture, environment, and human health. The existing methods have numerous shortcomings in determining gentamicin (GEN), a broad-spectrum antibiotic that causes nephrotoxicity and ototoxicity when found in excess. Here, an immunosensing platform to detect GEN using multiwalled carbon nanotubes (MWCNTs) and molybdenum disulfide (MoS₂) nanocomposite, deposited electrophoretically on indium tin oxide (ITO) glass has been developed. A novel 2-D graphene analog MoS₂@ MWCNTs nanocomposite was made via a facile and low-cost hydrothermal technique using l-cysteine to achieve remarkable electrochemical properties. Subsequently, a highly sensitive electrochemical immunosensor was fabricated by assembling monoclonal antibodies against gentamicin (anti-GEN) on a MoS₂@MWCNTs modified ITO electrode. The hetero-nanostructure formed on the immunosensor surface appeared relatively good conductor for accelerating the electron transfer. GEN was determined on anti-GEN modified electrodes by utilizing the differential pulse voltammetry technique by measuring the difference in current owing to the transfer of electrons directly between the redox species and immunoelectrodes. Under optimal experimental conditions, the fabricated immunosensor had a wide linear detection range of 1 × 10^?6–40 μg/mL, a high sensitivity of 13.55 μA (log μg/mL)^?1 and a low limit of detection and limit of quantification of 0.039 μg/mL and 0.130 μg/mL, respectively. The developed immunosensor also exhibits high reproducibility, repeatability, and good selectivity against various interferences. This electrochemical immunosensor having MoS₂ modified MWCNTs displays the excellent potential for the point-of-care device for GEN testing.     

Amperometric determination of NADH at a Nile blue/ordered mesoporous carbon composite electrode

A novel amperometric NADH sensor was presented based on a Nile blue A (NB)/ordered mesoporous carbon (OMC) composite (NB/OMC) electrode. Cyclic voltammetric tests revealed the NB/OMC displayed a new well defined redox couple in the potential range of ?250 to 50 mV in pH 6.85 phosphate buffer. Interestingly, we found that only the new redox couple exhibited significant catalytic activity towards the oxidation of NADH. Under a lower operation potential of ?0.1 V, NADH could be linearly detected up to 350 μM with an extremely lower detection limit of 1.2 μM (S/N = 3).     

Electrochemical detection of perchloroethylene using differential pulse voltammetry

We demonstrate the application of differential pulse voltammetry (DPV) for the electrochemical detection of perchloroethylene (PCE) on an unmodified glassy carbon electrode surface. Detection sensitivity was substantially improved using DPV, in which dechlorination was denoted by a cathodic peak observed at approximately − 0.6 V (vs Ag/AgCl). Peak current intensity was found to correlate linearly with concentration over a tested range of 0 to 10 μM. The utility of this technique was subsequently evaluated for PCE-spiked environmental samples containing either Methylobacterium adhaesivum (1 × 10⁶ cells/mL) or creek water (10% v/v). In all environmental samples, a linear dynamic range was also observed from approximately 0 to 10 μM. The limit of detection was determined to be 0.3 μM in blank buffer, 0.4 μM in bacteria-containing samples and 1.2 μM in creek water samples.