Electrochemical Sensor Research Articles

A novel electrochemical sensor based on a Cu-coordinated molecularly imprinted polymer and MoS2 modified chitin-derived carbon for selective detection of dextromethorphan.

Dextromethorphan (DXM) is a widely utilized central antitussive agent, which is frequently abused by individuals seeking its recreational effect. But DXM overdose can cause some adverse effects, including brain damage, loss of consciousness, and cardiac arrhythmias, and hence its detection is significant. Herein, an electrochemical sensor based on a Cu-coordinated molecularly imprinted polymer (Cu-MIP) was fabricated for its detection. For constructing the sensor, nitrogen-doped carbon nanosheets (CCNs) were prepared through calcining chitin under an argon atmosphere, and molybdenum disulfide (MoS2) was allowed to grow on their surface. Subsequently, the obtained MoS2/CCNs composite was employed to modify a glassy carbon electrode (GCE), and the Cu-MIP was electrodeposited on the electrode in a Cu-1,10-phenanthroline (Cu-Phen) solution containing DXM, where Cu2+ played a role in facilitating electron transfer and binding DXM. Due to the large specific surface area, good electrocatalytic properties and recognition of the resulting composite, the resulting Cu-MIP/MoS2/CCNs/GCE showed high selectivity and sensitivity. Under optimized experimental conditions, the peak current of DXM and its concentration exhibited a good linear relationship over the concentration range of 0.1-100 μM, and the limit of detection (S/N = 3) was 0.02 μM. Furthermore, the electrochemical sensor presented good stability, and it was successfully used for the determination of DXM in pharmaceutical, human serum and urine samples.

One-Pot Synthesis of Nanoflower-Like Zn2SnS4 as Nanozymes for Highly Sensitive Electrochemical Detection of H2O2 Released by Living Cells.

The sensitive and reliable nanozyme-based sensor enables the detection of low concentrations of H2O2 in biological microenvironments, it has potential applications as an in-situ monitoring platform for cellular H2O2 release. The uniformly dispersed bimetallic sulfide (Zn2SnS4) nanoflowers were synthesized via a one-pot hydrothermal method and the two kinds of metal ions can serve as morphology and structure directing agents for each other in the synthetic process. The nanoparticles were utilized as nanozyme materials to fabricate a novel electrochemical sensor, and it exhibits a distinct electrochemical response towards H2O2 with excellent stability and detection capability (with a minimum detection limit of 1.79 nM (S/N=3)), the excellent characteristics facilitate the precise detection of low concentrations of H2O2 in biological microenvironments. Use the macrophages differentiated from leukemia THP-1 cells as a representative sensing model, the sensor was successfully utilized for real-time monitoring of the release of H2O2 induced by living cells, which has significant potential applications in clinical diagnosis and cancer treatment.

Plant-based zinc nanoflowers assisted molecularly imprinted polymer for the design of an electrochemical sensor for selective determination of abrocitinib

The first electrochemical sensor application in the literature is described for the sensitive and selective determination of the selective Janus kinase (JAK)-1 inhibitor abrocitinib (ABR). ABR is approved by the U.S. Food and Drug Administration (FDA) for the treatment of atopic dermatitis. The molecularly imprinted polymer (MIP)-based sensor was designed to incorporate zinc nanoflower (ZnNFs)-graphene oxide (GO) conjugate (ZnNFs@GO), synthesized from the root methanolic extract (RME) of the species Alkanna cappadocica Boiss. et Bal. to improve the porosity and effective surface area of the glassy carbon electrode (GCE). Furthermore, the MIP structure was prepared using ABR as a template molecule, 4-aminobenzoic acid (4-ABA) as a functional monomer, and other additional components. Scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) were used to characterize the surface and structure of the synthesized nanomaterial and MIP-based surface. Among the electrochemical methods, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were preferred for detailed electrochemical characterization, and differential pulse voltammetry (DPV) was preferred for all other electrochemical measurements using 5.0 mM [Fe(CN)6]3–/4– solution as the redox probe. The MIP-based sensor, which was the result of a detailed optimization phase, gave a linear response in the 1.0 × 10–13 – 1.0 × 10–12 M range in standard solution and serum sample. The obtained limit of detection (LOD) and limit of quantification (LOQ) values and recovery studies demonstrated the sensitivity, accuracy, and applicability of the sensor. Selectivity, the most important feature of the MIP-based sensor, was verified by imprinting factor calculations using ibrutinib, ruxolitinib, tofacitinib, zonisamide, and acetazolamide.Graphical

Surface-display Techniques in Electrochemical Biosensor Designs for Health Monitoring

Abstract Enzymatic and microbial electrochemical biosensors integrate enzymes and microorganisms as biological recognition elements into the sensor design and functionality. Enzyme-based sensors offer high sensitivity and selectivity for target analyte detection. However, these have limited stability necessary for continuous analyte monitoring. Contrarily, microbe-based electrochemical sensors provide a means for continuous analyte sensing but are associated with challenges related to analyte selectivity in complex samples. To address these limitations, surface-display methods, which bind enzymes to microbial surfaces, enhance biosensor selectivity and sensitivity. This perspective outlines the application of surface-display techniques, offering a promising avenue for health monitoring.

Electrochemical Performance of Polyaniline‐Polyvanadate‐Copper Nanomaterials for the Detection of Benzoic Acid

AbstractThe introduction of nanomaterials as modified electrode materials into the field of electrochemical sensing is expected to improve the reliability, sensitivity, selectivity and repeatability of electrochemical sensors in detecting pollutants in the water environment. In this study, copper vanadate nanomaterials (Cu3V2O7(OH)2·2H2O, referred to as CVO) and Cu3V2O7(OH)2·2H2O/polyyaniline (PANI) composite nanomaterials (referred to as CVO/PANI) were successfully prepared and characterized by Fourier transform infrared spectrum (FTIR), X‐ray traveling‐action (XRD), scanning electron microscopy (SEM) and high‐resolution transmission electron microscopy (HR‐TEM).The modified glassy carbon electrodes (GCE) with these two materials were used for the detection of benzoic acid (BA) and exhibited excellent electrochemical sensing performance. The results show that two pairs of semi‐reversible redox peaks exist in both CVO and CVO/PANI modified glassy carbon electrode (GCE) in BA solution. The linear range of CVO and CVO/PANI nanomaterials‐modified GCE was 0.01‐2 mM and 0.001‐2 mM, and the limits of detection were 2.16 µM and 0.41 µM, respectively. Polyaniline plays important role in the electrochemical responses of BA at CVO/PANI modified GCE. PANI enhancedthe intensities of CV peaks and electrochemical determination ability for BA.This article is protected by copyright. All rights reserved

LDH-Based Voltammetric Sensors

Layered double hydroxides (LDHs), also named hydrotalcite-like compounds, are anionic clays with a lamellar structure which have been extensively used in the last two decades as electrode modifiers for the design of electrochemical sensors. These materials can be classified into LDHs containing or not containing redox-active centers. In the former case, a transition metal cation undergoing a reversible redox reaction within a proper potential window is present in the layers, and, therefore, it can act as electron transfer mediator, and electrocatalyze the oxidation of an analyte for which the required overpotential is too high. In the latter case, a negatively charged species acting as a redox mediator can be introduced into the interlayer spaces after exchanging the anion coming from the synthesis, and, again, the material can display electrocatalytic properties. Alternatively, due to the large specific surface area of LDHs, molecules with electroactivity can be adsorbed on their surface. In this review, the most significant electroanalytical applications of LDHs as electrode modifiers for the development of voltammetric sensors are presented, grouping them based on the two types of materials.

Electrochemical Sensor Based on a MXene Nanosheet–Gold Nanourchin Hybrid as a Superoxide Dismutase Mimic for Real-Time Detection of Superoxide Anions Released from Living Cells

Electrochemical Sensor Based on a MXene Nanosheet–Gold Nanourchin Hybrid as a Superoxide Dismutase Mimic for Real-Time Detection of Superoxide Anions Released from Living Cells

Design and fabrication of an electrochemical sensor based on nanocomposite of dendritic polymer and reduced graphene oxide to measure sports nutrition lactate

Design and fabrication of an electrochemical sensor based on nanocomposite of dendritic polymer and reduced graphene oxide to measure sports nutrition lactate

Ultrasensitive and Highly Selective Detection of Staphylococcus aureus at the Single-Cell Level Using Bacteria-Imprinted Polymer and Vancomycin-Conjugated MnO2 Nanozyme.

Pathogenic bacterial infections, even at extremely low concentrations, pose significant threats to human health. However, the challenge persists in achieving high-sensitivity bacterial detection, particularly in complex samples. Herein, we present a novel sandwich-type electrochemical sensor utilizing bacteria-imprinted polymer (BIP) coupled with vancomycin-conjugated MnO2 nanozyme (Van@BSA-MnO2) for the ultrasensitive detection of pathogenic bacteria, exemplified by Staphylococcus aureus (S. aureus). The BIP, in situ prepared on the electrode surface, acts as a highly specific capture probe by replicating the surface features of S. aureus. Vancomycin (Van), known for its affinity to bacterial cell walls, is conjugated with a Bovine serum albumin (BSA)-templated MnO2 nanozyme through EDC/NHS chemistry. The resulting Van@BSA-MnO2 complex, serving as a detection probe, provides an efficient catalytic platform for signal amplification. Upon binding with the captured S. aureus, the Van@BSA-MnO2 complex catalyzes a substrate reaction, generating a current signal proportional to the target bacterial concentration. The sensor displays remarkable sensitivity, capable of detecting a single bacterial cell in a phosphate buffer solution. Even in complex milk matrices, it maintains outstanding performance, identifying S. aureus at concentrations as low as 10 CFU mL-1 without requiring intricate sample pretreatment. Moreover, the sensor demonstrates excellent selectivity, particularly in distinguishing target S. aureus from interfering bacteria of the same genus at concentrations 100-fold higher. This innovative method, employing entirely synthetic materials, provides a versatile and low-cost detection platform for Gram-positive bacteria. In comparison to existing nanozyme-based bacterial sensors with biological recognition materials, our assay offers distinct advantages, including enhanced sensitivity, ease of preparation, and cost-effectiveness, thereby holding significant promise for applications in food safety and environmental monitoring.

A novel low oxidation potential hydroxyurea sensor utilizing flower-shaped Zn and N co-doped porous carbon coupled with graphene oxide via one-step electrodeposition

Accurate monitoring of hydroxyurea (HU) dosage is imperative in the administration of anticancer drugs. Existing determination methods face challenges such as operational complexity, low sensitivity, or high oxidation potentials. In this study, a novel HU electrochemical sensor (Zn/N-PC/GO/GCE) was synthesized using flower-shaped Zn/N co-doped porous carbon (Zn/N-PC) with graphene oxide (GO) through a one-step electrodeposition. The sensor features a distinctive three-step oxidation process for HU with a low oxidation potential, attributed to an electrochemical activation electrode strategy and crucial Zn/N co-doping in Zn/N-PC. Three electrons involved oxidation process of HU and Zn/N-PC/GO adsorption energy through transferred electrons and density functional theory (DFT). Under optimized conditions, the sensor demonstrated a broad linear detection range (1–1000 μM) and an impressive limit of detection (LOD) of 0.52 μM. Applicability was confirmed by analyzing HU in tablet formulations, urine and serum samples. This study presents an innovative electrochemical method for accurate HU monitoring, elucidating a potential three-step oxidation mechanism.

A novel electrochemical sensor for the detection of metronidazole residues in food samples

The widespread use and misuse of antibiotics in pharmaceuticals and animal farming has resulted in their accumulation in food sources and the environment, posing significant threats to human health, the environment, and the global economy. In this study, we have developed a hypersensitive, and ultra-selective electrochemical sensor, the first of its kind, by integrating a thermally annealed gold-silver alloy nanoporous matrix (TA-Au-Ag-ANpM) with reduced graphene oxide (r-GO) and poly(glycine) at the surface of a glassy carbon electrode (GCE). This sensor aims to detect life-threatening metronidazole (MTZ) residues in food samples. TA-Au-Ag-ANpM/r-GO/poly(glycine)/GCE was thoroughly characterized using a range of analytical techniques, including UV–Vis, FT-IR, XRD, SEM, and EDX. Furthermore, its electrochemical properties were investigated by cyclic voltammetry (CV), square wave voltammetry (SWV), and electrochemical impedance spectroscopy (EIS). The sensor exhibited outstanding performance, with a broad linear range of 2.0 pM–410 μM. The limits of detection (LOD) and quantification (LOQ) were determined to be 0.0312 pM and 0.104 pM, respectively. The TA-Au-Ag-ANpM/r-GO/poly(glycine)/GCE exhibited exceptional reproducibility, repeatability, stability, and resistance to interferences. Moreover, the sensor demonstrated outstanding performance in detecting MTZ residues in milk powder, pork, and chicken meat samples, achieving very good recoveries (96.9%–101.4%) with a relative standard deviation (RSD) below 5%. This performance highlights the potential for practical applications in food safety and quality monitoring. Therefore, the developed sensor contributes to the advancement of electrochemical sensing technology and its application in ensuring food safety and integrity by combating antibiotic residues.

A highly stable electrochemical sensor with antifouling and antibacterial capabilities for mercury ion detection in seawater

The monitoring of heavy metal ions in ocean is crucial for environment protection and assessment of seawater quality. However, the detection of heavy metal ions in seawater with electrochemical sensors, especially for long-term monitoring, always faces challenges due to marine biofouling caused by the nonspecific adsorption of microbial and biomolecules. Herein, an electrochemical aptasensor, integrating both antifouling and antibacterial properties, was developed for the detection of Hg2+ in the ocean. In this electrochemical aptasensor, eco-friendly peptides with superior hydrophilicity served as anti-biofouling materials, preventing nonspecific adsorption on the sensing interface, while silver nanoparticles were employed to eliminate bacteria. Subsequently, a ferrocene-modified aptamer was employed for the specific recognition of Hg2+, leveraging the aptamer's ability to fold into a thymine-Hg2+-thymine (T-Hg2+-T) structure upon interaction, and bringing ferrocene nearer to the sensor surface, significantly amplifying the electrochemical response. The prepared electrochemical aptasensor significantly reduced the nonspecific adsorption in seawater while maintaining sensitive electrochemical response. Furthermore, the biosensor exhibited a linear response range of 0.01–100 nM with a detection limit of 2.30 pM, and realized the accurate monitoring of mercury ions in real marine environment. The research results offer new insights into the preparation of marine antifouling sensing devices, and it is expected that sensors with antifouling and antimicrobial capabilities will find broad applications in the monitoring of marine pollutants.

The Optimal Doping Ratio of Fe2O3 for Enhancing the Electrochemical Stability of Zeolitic Imidazolate Framework-8 for Energy Storage Devices

This paper aims to discover a novel composite material that has great potential for manufacturing high-performance supercapacitors suitable for diverse applications, such as electric vehicles, portable electronics, and stationary energy storage systems. Zeolitic imidazolate framework-8 (ZIF-8) doped by different concentrations up to 5 wt.% of nanosized Fe2O3 have been prepared (ZIF-8/Fe2O3). The effect of doping ratio 1, 3, and 5 wt.% on the structural and electrochemical properties of ZIF-8/Fe2O3 has been investigated. The structural characterization has been carried out using TGA, BET, XRD, and FTIR. The XRD analysis revealed that the crystalline size of our sample increased by approximately 16% as a result of doping ZIF-8 with 5 wt.% of Fe2O3. The structural analysis of the doped samples revealed that the material exhibited enhanced thermal stability and porosity, with an increase of approximately 105 m2/g. The introduction of doped nanometal oxides improved the capacitance value of ZIF-8 by significantly increasing its surface area. Additionally, the electron transport efficiency within ZIF-8/5 wt.% Fe2O3/electrode is increased. The Nyquist plot decreases as the doping of Fe2O3 increases. This indicates a decrease in the charge transfer resistance at the electrode–electrolyte interface, which is desired in applications such as batteries, fuel cells, or electrochemical sensors where faster electron transfer is needed for improved performance.

Electrochemical strategies for determination of tert-butyl hydroquinone (TBHQ) in food samples

AbstractTert-butyl hydroquinone (TBHQ) is a member of the synthetic phenolic antioxidant family that prevents the formation of free radicals and prevents radicals from damaging cells by trapping them. In addition, TBHQ is widely preferred as an additive in foods and vegetable oils because of its low cost and high chemical stability. TBHQ is not only a food preservative but is also frequently used as a stabilizer to prevent auto-polymerization in cosmetics, biodiesel, pharmaceuticals, coating products, and different application areas. TBHQ has been shown to cause diseases, such as DNA damage, carcinogenesis, and cell apoptosis, when administered at high doses. Excessive consumption of TBHQ causes adverse effects, such as stomach tumors, liver damage, and underdevelopment of the reproductive system. Different analytical methods have been used to detect TBHQ in food samples. The most important of these methods are traditional analytical methods such as chromatographic and spectrophotometric methods. However, these methods have basic shortcomings such as high analysis costs, long pre-processing, expensive equipment, need for many organic solvents, requiring expertise, and long detection times. In recent years, electrochemical sensors have attracted attention in the scientific world owing to their high sensitivity, fast analysis time, portability, low cost, and convenience of miniaturization. This review discusses electrochemical studies performed to date for the determination of TBHQ in food samples. The methods used in these studies have been evaluated in a wide range of aspects, such as the electrode, working range, detection limits, and analytical applications.

Underground Ink: Printed Electronics Enabling Electrochemical Sensing in Soil

Improving agricultural production relies on the decisions and actions of farmers and land managers, highlighting the importance of efficient soil monitoring techniques for better resource management and reduced environmental impacts. Despite considerable advancements in soil sensors, their traditional bulky counterparts cause difficulty in widespread adoption and large-scale deployment. Printed electronics emerge as a promising technology, offering flexibility in device design, cost-effectiveness for mass production, and a compact footprint suitable for versatile deployment platforms. This review overviews how printed sensors are used in monitoring soil parameters through electrochemical sensing mechanisms, enabling direct measurement of nutrients, moisture content, pH value, and others. Notably, printed sensors address scalability and cost concerns in fabrication, making them suitable for deployment across large crop fields. Additionally, seamlessly integrating printed sensors with printed antenna units or traditional integrated circuits can facilitate comprehensive functionality for real-time data collection and communication. This real-time information empowers informed decision-making, optimizes resource management, and enhances crop yield. This review aims to provide a comprehensive overview of recent work related to printed electrochemical soil sensors, ultimately providing insight into future research directions that can enable widespread adoption of precision agriculture technologies.

One-step growth of Cu-doped carbon dots in amino-modified carbon nanotube-modified electrodes for sensitive electrochemical detection of BPA.

Copper-doped carbon dots and aminated carbon nanotubes (Cu-CDs/NH2-CNTs) nanocomposites were synthesized by a one-step growth method, and the composites were characterized for their performance. An electrochemical sensor for sensitive detection of bisphenol A (BPA) was developed for using Cu-CDs/NH2-CNTs nanocomposites modified with glassy carbon electrodes (GCE). The sensor exhibited an excellent electrochemical response to BPA in 0.2M PBS (pH 7.0) under optimally selected conditions. The linear range of the sensor for BPA detection was 0.5-160μM, and the detection limit (S/N = 3) was 0.13μM. Moreover, the sensor has good interference immunity, stability and reproducibility. In addition, the feasibility of the practical application of the sensor was demonstrated by the detection of BPA in bottled drinking water and Liu Yang River water.

An electrochemical sensor based on electrochemically activated carbon cloth and poly (o-aminothiophenol) cross-linked nanogold imprinted layer for the determination of tert-butylhydroquinone

In this study, an electrochemical sensor based on MoS2 with enhanced electrochemical signals from electrochemically activated carbon cloth (EACC) electrodes and cross-linked o-aminothiophenol functionalized AuNPs (o-ATP@AuNPs) was developed for the detection of the unsaturated vegetable oil antioxidant tert-butylhydroquinone (TBHQ). In this approach, carbon cloth is activated through the implementation of electrochemical methods, thereby effectively increasing its specific surface area. The resulting EACC, serving as an electrode substrate, enables the growth of additional nanomaterials and enhances conductivity. The incorporation of MoS2 effectively augments the sensitivity of the electrochemical sensor. Subsequently, MIP/MoS2/EMCC is formed via electropolymerization, utilizing TBHQ as the template molecule and o-ATP@AuNPs as the functional monomer. The SS bond of o-ATP ensures a strong and stable connection between MoS2 and o-ATP@AuNPs, thereby facilitating the immobilization of MIP. In addition, the high conductivity possessed by o-ATP@AuNPs could effectively improve the sensitivity of the electrochemical sensor. Under the optimal conditions, MIP/MoS2/EMCC could determine TBHQ in the range of 1 × 10−3 μM to 120 μM by differential pulse voltammetry (DPV) with a detection line of 0.72 nM. The proposed MIP/MoS2/EMCC is expected to be applied in the future for the selective and sensitive detection of TBHQ in vegetable oils.

An R-type hexagonal ferrite nanoparticles-based electrochemical sensor for Levofloxacin detection in pharmaceutical and clinical specimens

The usage of Levofloxacin (LEV) has increased in recent years for the treatment of bacterial infections in both human and veterinary fields. In this context, there has been a significant demand for the development of a highly sensitive and cost-effective approach to LEV quantification. In this study, R-type hexagonal ferrite nanoparticles (SrSn2Fe4O11-NPs) were prepared by an auto-ignition methodology and various analytical techniques were used for the materiaĺs characterization, including X-ray diffraction (XRD), Field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), Brunauer Emmett and Teller (BET) analysis, dynamic light scattering (DLS), and vibrating sample magnetometer (VSM) analysis. The characterization confirmed that the prepared material has a crystalline structure single-phase with a crystalline size of 35.02 nm. The R-type hexagonal ferrite nanoparticles were immobilized on a glassy carbon electrode (GCE) by a simple drop-casting approach to developing an efficient electrochemical sensor (SrSn2Fe4O11-NPs/GCE) for sensitive and selective LEV detection through an extended concentration range (0.06 × 10−6 to 170 × 10−6 M) and a low detection limit of (41.5nM). The developed sensor was applied successfully to quantitatively determine LEV in clinical samples and pharmaceutical preparations with excellent recoveries from 95.2 to 102.5 %.

An antifouling electrochemical sensor integrating ‘‘3-in-1″ dual-targeted aptamer for the detection of the SARS-CoV-2 spike protein

Electrochemical biosensors have shown promise in bioanalysis and diagnosis. However, they suffer from the accumulation and adhesion of biomolecules in biofluids on sensing surfaces, while the hiring of potential antifouling is limited by the cost and complexity of the construction methods. Here, an economical three-dimensional (3D) conductive antifouling coating was prepared. This coating was composed of bovine serum albumin (BSA) crosslinked glutaraldehyde (GA) and copper-gold nanowires (CuAu NWs) with excellent electrical conductivity. Furthermore, a dual-targeted aptamer (D-Apt), with a “3-in-1″ structure of two specific binding sequences and a DNA linker, was designed to specifically recognize BSA and the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) spike (S) protein, affording low nanomolar binding affinity. Importantly, the introduction of the D-Apt greatly simplified the functionalization procedure on the electrode surface and the immobilization of the biorecognition element. Then, a simple electrochemical biosensor based on the CuAu/BSA/GA and D-Apt was constructed for the detection of S protein. This sensor exhibited merits of cost-effectiveness, sensitivity and practicality for detection of S protein. The work could provide a facile avenue to construct electrochemical biosensors with low-cost antifouling for the accurate diagnosis of epidemic antigenic disease markers.

An antifouling electrochemical biosensor using self-signal for Salmonella typhimurium direct detection in food sample

Eating food contaminated by foodborne pathogens can lead to illness. The development of electrochemical sensors for pathogen detection has received widespread attention. However, the analytical performance of electrochemical sensors is inevitably affected by the non-specific adsorption of molecules in the sample. Moreover, the external signal probes might be affected by the complex components in the sample accompanied with signal suppression. This work presents an electrochemical aptasensor for Salmonella typhimurium detection based on the self-signal of poly-xanthurenic acid and the antifouling ability of chondroitin sulfate. The detection time was 60 min. The linear range was from 101 to 107 CFU/mL, and the detection limit was 3 CFU/mL. The biosensors presented good repeatability and storage stability. And the biosensors has been successfully applied in milk and orange juice. This strategy is expected to be applied in the design of other antifouling biosensors, to achieve rapid detection of pathogens and ensure food safety.