Electrochemical Sensor Research Articles

An o-Phenylenediamine and MWCNT-Based Electrochemical Sensor for the Detection of Triclosan by Cyclic Voltammetry

Selectivity and sensitivity are the two key parameters for construction of a sensor. In this work, a novel electrochemical sensor based on molecularly-imprinted composites synthesized from o-phenylenediamine (o-PD) and multiwalled carbon nanotube (MWCNT) to detect triclosan is reported. Two different sensors were developed MIC/GC and MIC/cf-MWCNT/GC. To fabricate MIC/GC, molecularly imprinted composite (MIC) was synthesized by cyclic voltammetry using o-PD, COOH-functionalized MWCNT (cf-MWCNT) and triclosan on glassy carbon (GC) electrode, following removal of surface triclosan. MIC/cf-MWCNT/GC was fabricated by synthesizing MIC on cf-MWCNT coated GC. Template removal was performed using NaOH solution. MIC/GC could detect triclosan till 40 ppb while using MIC/cf-MWCNT/GC, 10 ppb of limit of detection (LOD) was achieved. Adsorption isotherms were constructed for both the films. Langmuir adsorption isotherm gave the best fit for MIC/cf-MWCNT/GC with -ΔGads value of 54.952 kJ mol−1 indicating stronger chemisorption. To understand the role of cf-MWCNT in detection of triclosan, electrochemical band gap studies, electrochemical impedance spectroscopy, and cyclic voltammetry studies were conducted. Both the sensors were found to be efficient for detection of triclosan in the presence of interfering ions.

An electrochemical sensor based on molecularly imprinted poly(o-phenylenediamine) for the detection of thymol

A molecularly imprinted electrochemical sensor was facilely fabricated for the detection of thymol (THY). o-Phenylenediamine (oPD) was used as the functional monomer and electropolymerized on the surface of the glassy carbon electrode (GCE) by using THY as the templates. After the THY templates were removed with 50 % (v/v) ethanol, imprinted cavities complementary to the templates were formed within the poly(o-phenylenediamine) (PoPD) films. The resultant molecularly imprinted PoPD/GCE (MI-PoPD/GCE) was used for the detection of THY, and a wide linear range from 0.5 to 100 μM with a low limit of detection (LOD) of 0.084 μM were obtained under the optimal conditions. The developed MI-PoPD/GCE also displays high selectivity, reproducibility and stability for THY detection. Finally, the content of THY in the real samples was accurately determined by the as-fabricated MI-PoPD/GCE, demonstrating its high practicability and reliability.

Aminosilane assisted deposition of gold nanoparticles on Zn(OH)2 nanosheets and their application in electrochemical sensor

A facile and efficient method for systematical deposition of gold nanoparticles (AuNPs) on Zn(OH)2 nanosheets (NS) with different Zn and Au ratios was established in the presence of N-[3-(trimethoxysilyl)propyl]diethylenetriamine (TPDT silane), without adding any external reducing agents, at room temperature. Here, TPDT silane behaves as both a stabilizing and reducing agent. UV–vis absorption spectroscopy, transmission electron microscopy, high-angle annular dark-field scanning transmission electron microscopy-energy dispersive X-ray spectroscopy, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy were used to confirm the formation of AuNPs on Zn(OH)2 NS. As the concentration of AuNPs increased, a proportional increase in both the number and size of deposited AuNPs on Zn(OH)2 NS was observed. To understand how the variation in the number and size of AuNPs affects their catalytic activity, the electrocatalytic activity of different composition ratios of Zn(OH)2-Au NS toward nitrite ions was studied using cyclic voltammetry and amperometric technique. The TPDT-stabilized Zn(OH)2-Au NS showed high electrocatalytic activity, attributed to the effective electron transfer from Zn(OH)2 NS to AuNPs, creating a synergistic effect that enhances the overall activity. The optimal Zn(OH)2-Au NS modified electrode showed an amperometric sensitivity of 5.72 nA/µM and a limit of detection of 1.2 µM for nitrite ions in water sample well below the guideline value of WHO. This demonstrates the practical applicability of this method for real-world water analysis.

Development of an efficient electrochemical sensor based on CuAl-LDH using an electrostatic repulsion approach for the selective determination of dopamine in the presence of uric acid and ascorbic acid species

This study provides a unique electrochemical sensor that exhibits both excellent sensitivity and selectivity, while also being environmentally friendly. The CuAl-LDH/GCE sensor, proposed as the recommended sensor, was synthesized using a straightforward one-step co-precipitation procedure. It was first used to measure dopamine levels using differential pulse voltammetry. At the ideal pH level of 8, dopamine has a positive charge, but ascorbic acid and uric acid have a negative charge. LDH, on the other hand, carries a negative charge and exhibits high electrostatic attraction towards dopamine, but is electrostatically repelled by negatively charged ascorbic acid and uric acid. Hence, CuAl-LDH/GCE has the potential to specifically ascertain the existence of dopamine in the presence of these particular species. The examination of the composition and morphology of CuAl-LDH was conducted using various analytical techniques, including scanner electron microscopy (FESEM), transmission electron microscope (TEM), element mapping (MAP), Fourier transform infrared (FTIR), energy-dispersive X-ray spectroscopy (EDX), Brunauer Emmett Teller (BET), X-ray photoelectron diffraction (XRD), and Raman techniques. Under ideal circumstances, the calibration graph of dopamine was generated using differential pulse voltammetry. A linear range of 4.194–1151.54 μM was achieved for dopamine, with a limit of detection of 0.33 μM. The findings of the study indicate that the sensor created for dopamine determination has exceptional stability, repeatability, and reproducibility. The sensor that was presented was effectively used for the measurement of dopamine in both pharmaceutical ampoules and human plasma samples.

Graphene quantum dots (GQDs)-modified screen-printed electrode for the determination of cannabidiol (CBD) in hemp seeds flour

In this work, the development of a graphene quantum dots (GQDs)-modified screen-printed carbon (SPCE) electrode for the determination of cannabidiol (CBD), a cannabinoid present in the Cannabis L. Sativa (hemp) plant, is reported. This cannabinoid is non-intoxicating and non-psychoactive, thus CBD-containing drugs as well as CBD-containing foods, are now on the market in many countries due to their health-beneficial effects and pharmacological activities. Because of the increasing interest in analyzing CBD in these real samples, we analyzed here a sample of hemp flour that was used for testing the developed CBD electrochemical sensor. Preliminary work devoted to optimizing the analysis conditions, allowed to development of a GQDs-modified electrode with promising characteristics for the simple screening of CBD. The electroanalytical tests for CBD detection showed a sensitivity of 0.98 μAμM-1 cm−2, which is increased by 2-folder compared to bare SPCE, and a limit of detection (LOD) equal to 0.277 μM. The developed GQDs/SPCE sensor and the analysis procedure were then applied for the CBD analysis in a hemp seeds flour sample. Based on the results obtained, the advantages/disadvantages evidenced by operating with the developed electrochemical sensor in the analysis of CBD in real samples were discussed.

Enzyme-Free Glucose Detection via Scalable and Economical Fabrication of Nickel-Polyvinylpyrrolidone-Modified Multi-Walled Carbon Nanotubes

Development of accurate, reliable, and affordable glucose detection tools remains a top scientific priority. Nanotechnology is frequently utilized for this purpose. In this study, polyvinylpyrrolidone (PVP)-modified nickel (Ni) nanoparticles on multi-walled carbon nanotube (MWCNT) were prepared using a unique microwave synthesis technique. The synthesized particles were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). TEM analysis revealed that well-dispersed Ni nanoparticles with an average size of about 4.11 nm were uniformly dispersed on the MWCNT surface in the presence of PVP particles. The obtained NiPVP@MWCNT was used for the glucose sensor and its performance was investigated. According to the results, the limit of detection (LOD) and limit of quantification (LOQ) values for NiPVP@MWCNT nanocomposite in the linear range of 0.1 mM - 1 mM were calculated as 0.364 mM and 1.215 mM, respectively. As a result of the selectivity test, it was observed that it was highly selective for glucose and the current values increased with increasing concentration. Our study shows that the cost of platinum, which is widely used in electrochemical sensors, can be reduced by the application of polymeric structures. This leads to a more stable structure. The developed nanostructures are efficient, highly stable, discriminative, and sensitive and have the potential to be used as glucose sensors in the market.

Natural deep eutectic solvent-supported exfoliated graphite nanoplatelet-based electrochemical sensor for the determination of tyramine in fermented beverages

A novel electrochemical sensor was developed for the determination of tyramine. The sensor was constructed by modifying the surface of a glassy carbon electrode (GCE) with a film composed of exfoliated graphite nanoplatelets (xGnPs) dispersed in a natural deep eutectic solvent (NADES). The NADES was prepared by simply mixing equimolar amounts of caprylic acid and menthol and heating at 80 °C for 30minutes. Characterization studies confirmed the formation of a NADES through the attenuated total reflectance-Fourier transform infrared spectroscopy technique, while transmission electron microscopy demonstrated the ability of the NADES to disperse the xGnPs. Electrochemical impedance spectroscopy data showed that the modified sensor exhibited lower resistivity than the unmodified electrode. By optimizing the parameters of square wave voltammetry and experimental conditions to obtain the highest peak current values for tyramine oxidation, a calibration curve was constructed in a 0.1molL−1 phosphate buffer (pH 7.0), obtaining detection and quantification limits of 0.06 and 0.20mgL−1, respectively. Finally, the sensor was successfully applied to the determination of tyramine in fermented milk, beer, and non-alcoholic beer samples, with satisfactory recovery data.

Gold nanoparticle-mediated molecularly imprinted electrochemical sensor MIP/AuNPs/GCE for highly sensitive and selective detection of neutral phosmet residues in fruits and vegetables

A novel electrochemical sensor MIP/AuNPs/GCE was developed by depositing gold nanoparticles and electropolymerizing molecularly imprinted film on the surface of glassy carbon electrode (GCE) for highly sensitive detection of neutral phosmet residues in fruits and vegetables. Scanning electron microscopy, energy dispersive spectroscopy, atomic force microscopy, cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the imprinted sensor. The results showed that the imprinted film on GCE was evenly prepared with better specific recognition of phosmet on MIP/AuNPs/GCE than that on bare GCE. Several parameters including deposition time, functional monomer and its molar ratio, scanning cycles, and elution time were optimized in detail. The linear range of the MIP/AuNPs/GCE prepared in this work was 0.020–4.0 nmol/L with limit of detection of 0.010 nmol/L, which was much lower than MIP/GCE (0.17 nmol/L). The identification mechanism of MIP/AuNPs/GCE for phosmet was also confirmed as adsorption-diffusion model with effective surface area increasing after mediated by AuNPs. Selectivity, reproducibility and repeatability of the MIP/AuNPs/GCE were acceptable. The recovery of applying the sensor to detect PM in real samples ranged from 91.40 % to 107.3 %, which agreed well with those of HPLC. The method of developing MIP/AuNPs/GCE sensor herein could be extended to detecting other neutral pesticide residues in food and environment.

Mxene-derived Na2O7Ti3 nanoribbon as a promising electrode material for the detection of ethyl paraoxon in complex matrices

This study reports the development of MXene (Ti3C2Tx) derived sodium titanate nanoribbon-based electrochemical sensor for pesticide detection. Titanium Carbide (Ti3C2) MXene-derived sodium titanate nanoribbon (MNR) was obtained by facile hydrothermal synthesis and characterized by powder X-ray Diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray analysis(EDS) and, high-resolution transmission electron microscopy (HR-TEM). The synthesized water-dispersed MNR was stabilized with Nafion and deposited on the surface of glassy carbon electrodes (GCE), which provide a symmetrical uniform electrode surface. Further, the electrodes were electrochemically characterized with cyclic voltammetry (CV), differential pulse voltammetry (DPV), linear sweep voltammetry(LSV), and electrochemical impedance spectroscopy (EIS). The electrochemical sensing of ethyl paraoxon was carried out in 0.1 M phosphate buffer (PB) by CV, LSV, and DPV. The developed electrochemical sensor exhibited a limit of detection (LOD) of 0.22 nM, a very wide detection range from 0.69 nM to 174.03 nM, and a reliable sensitivity of 0.707 µA/nM/cm2. Moreover, the developed sensor was also employed for the detection of ethyl paraoxon in real samples (vegetable extract spiked with the pesticide). The results suggest that the developed MNR-based sensor would be a potential approach for efficient and accurate detection of ethyl paraoxon in ambient samples, with minimal interference.

Sensitive sensing of GLA and ISL based on highly conductivity nitrogen-doped carbon synergistic dual-template molecularly imprinted ratiometric electrochemical sensor

A novel ratiometric Molecularly Imprinted Electrochemical sensor for the specific marker of Glycyrrhiza glabra L. was developed in this work. To achieve simultaneous detection of two analytes on one sensor, we constructed a double template molecular imprinted electrochemical sensor with glabridin (GLA) and isoliquiritin (ISL) as templates. Further, Ferrocene/ZIF-8 (Fc/ZIF-8) composites were prepared via a one-pot solvothermal reaction and coated on the surface of a glassy carbon electrode (GCE), and the oxidation of Fc was presented as the internal reference signal. Nitrogen-doped carbon (NOC) with high conductivity was further loaded on the modified GCE. Based on theoretical exploration and computer directional simulation of density functional theory (DFT), the optimal functional monomer and the best ratio of double template molecules to functional monomer were screened. Under optimal conditions, the sensor produced electrochemical curves when exposed to a solution containing GLA and ISL. As the concentration of GLA and ISL increased, the peak current intensity of GLA and ISL (IGLA and IISL) also increased, while the peak current intensity of Fc (as a reference signal) remained relatively constant. The values of IGLA/IFc and IISL/IFc showed excellent linear relationships with GLA and ISL concentrations in the range of 0.1-160 μM and 0.5-150 μM, respectively. The detection limits were 0.052 μM and 0.27 μM (S/N=3), respectively. Due to the imprinting effect of MIP and the existence of a reference signal, the sensor exhibited excellent selectivity and anti-interference ability and was successfully applied to the quality evaluation of Glycyrrhiza glabra L..

Research Progress in the Detection of Aflatoxin B1 Based on Aptamers

Abstract: Aflatoxin B1 is highly toxic, mutagenic, teratogenic, and carcinogenic and is a class I carcinogen. Peanuts, cotton, and corn may be affected by AFB1 during cultivation, which can seriously jeopardize human health. Developing a simple, sensitive, and selective method for detecting AFB1 is imminent. Aptamers are obtained through in vitro screening of ligands by single-stranded oligonucleotides (DNA or RNA) through exponential enrichment (SELEX) technology. As emerging highly selective recognition molecules, they have the advantages of strong affinity, good stability, and strong specificity. Because it does not have the function of signal conversion, it cannot produce physicochemical signals that can be detected in the process of specific binding with target molecules, so it is necessary to convert the process of specific binding of aptamers to target molecules into a process of easily detectable physicochemical signal changes. According to different conversion methods, aptamer biosensors are divided into electrochemical aptamer sensors, fluorescent aptamer sensors, colorimetric aptamer sensors, surface Raman-enhanced aptamer sensors, and so on. Herein, the recent progress and application of aflatoxin B1 detection by nucleic acid aptamer biosensors based on the above signals are reviewed, and the future development prospects and challenges of this kind of biosensor are summarized.

Hydrodynamics-engineered polyaniline nanofibers on graphene nanosheets for high-performance pH sensors

Real-time sweat monitoring in the human body using wearable sensors is promising for noninvasive and continuous healthcare applications. For reliable and accurate sweat analysis, further improvement in the response time and long-term stability of sensors is required. This paper reports an electrochemical pH sensor based on polyaniline/graphene (PANi-Gr) with rapid electron and ion transfer. The implementation of the Taylor–Couette flow approach allowed the efficient exfoliation of graphite into Gr nanosheets and the rapid polymerization of aniline monomers on the Gr surface, resulting in nanofiber PANi-deposited Gr nanocomposites. PANi-Gr had a large surface area and porous structure, which are favorable for rapid and stable electrochemical reactions. The screen-printed PANi-Gr-based pH sensor exhibited a Nernstian sensitivity of 61.91mV/pH, rapid response time of <1s, and long-term stability upon monitoring with minimal potential drift (0.04mVh−1) under strong acidic and basic conditions. Furthermore, the on-body performance of the wearable pH sensor integrated with a wireless electronic device was analyzed via the noninvasive real-time monitoring of human sweat pH during stationary cycling. The developed sensor can be used in wearable real-time sweat monitoring devices for medical and healthcare applications.

Propionate outperforms conventional acetate as electron donors for highly-sensitive electrochemical active biofilm sensors in water biotoxicity early-warning

With the ability to generate in situ real-time electric signals, electrochemically active biofilm (EAB) sensors have attracted wide attention as a promising water biotoxicity early-warning device. Organic matters serving as the electron donors potentially affect the electric signal’s output and the sensitivity of the EAB sensor. To explore the influence of organic matters on EAB sensor’s performance, this study tested six different organic matters during the sensor’s inoculation. Besides the acetate, a conventional and widely used organic matter, propionate and lactate were also found capable of starting up the sensor. Moreover, the propionate-fed (PF) sensor delivered the highest sensitivity, which are respectively 1.4 times and 2.8 times of acetate-fed (AF) sensor and lactate-fed (LF) sensor. Further analysis revealed that EAB of PF sensor had more vulnerable intracellular metabolism than the others, which manifested as the most severe energy metabolic suppression and reactive oxygen species attack. Regarding the microbial function, a two-component system that was deemed as an environment awareness system was found in the EAB of PF, which also contributed to its high sensitivity. Finally, PF sensor was tested in real water environment to deliver early-warning signals.

The layer-by-layer assembled ERGO+/ERGO− multilayer modified electrode for sensitive detection of dopamine

Graphene materials represented by graphene oxide (GO) have been widely regarded as functional coatings or films to modify surface of the electrode for detecting dopamine molecules. However, interfacial material properties for detection sensitivity, film stability, and applicability to electrodes are still highly desired. Herein, we first present a screen-printing carbon electrode (SPCE) coated with an electrochemically reduced layer-by-layer (LbL) assembled multilayer driven by an electrostatic interaction between positively charged polyethyleneimine-modified GO with amine groups (ERGO+) and negatively charged carboxyl-functionalized GO (ERGO−), which is briefly described as (ERGO+/ERGO−)n/SPCE. Firstly, without using conventional glassy carbon and gold electrodes, SPCE was tried to make coatings adapt to more flexible and unstable electrodes, simultaneously guaranteeing higher detection performance. Secondly, although a variety of electrochemical sensors such as GO−/SPCE and ERGO−/SPCE were obtained through the drop-casting technique, as-prepared (ERGO+/ERGO−)n/SPCE showed much higher electrocatalytic activities with enhanced peak current signals and reduced charge transfer resistance. Finally, excellent electrochemical properties and sensing performances of the (ERGO+/ERGO−)n/SPCE sensor for detection of dopamine were demonstrated, especially having a linear range of 1 μM to 1000 μM. Meanwhile, the detection limit is as low as 0.39 μM and S/N is equal to 3. The present work offers a potential direction to develop GO modified electrodes for sensitive biomolecular detection.

Sensitive electrochemical biosensor for rapid detection of sEV-miRNA based turbo-like localized catalytic hairpin assembly

Small extracellular vesicle-associated microRNAs (sEV-miRNAs) have emerged as critical biomarkers for cancer diagnosis, yet the rapid detection of these low-abundance molecules in clinical samples remains a formidable challenge. Herein, a simple turbo-like localized catalytic hairpin assembly (TL-CHA) was proposed for sEV-miR-1246 measurement. This electrochemical sensor achieves dual localization through the ingeniously use of AuNPs and DNA nanowires, which provides rich sites for CHA cascade amplification, significantly enhancing the effective reaction and amplify the detection response. Leveraging this innovative design, this biosensor demonstrated the ability to detect sEV-miRNA at concentrations as low as 5.24 aM in a time frame of 30 min. The precision of the measurements was validated through reverse transcription quantitative polymerase chain reaction. Furthermore, the sensor was used for analyzing plasma samples from gastric cancer patients yielded AUC values of 0.973 for all stages and 0.945 for early stages. This demonstrates the sensor's robust performance in both the staging diagnosis and early screening of gastric cancer. Therefore, this platform has great potential for the clinical cancer diagnosis.

Facile fabrication of liquid metal enabled conductive zwitterionic hydrogel for robust electrochemical sensing in complex serum

Any materials present in complex samples that bind the sensing interface non-specifically will greatly decrease the sensitivity and accuracy of the electrochemical sensor. Zwitterionic hydrogel have exhibited extraordinary antifouling ability, but they are limited by the electrical insulativity and weak interface, resulting in a double-edged strategy. Herein, we proposed a novel approach to resolve this challenge thanks to the liquid metal (LM). It was found that with only ultrasonic treatment, a core–shell nanostructure could be easily formed between LM matrix and sodium alginate (SA) polymer, accompanied with the generation of lots of free radical, which initiated the polymerization of zwitterionic monomer and further crosslinking with methylacrylated bovine serum albumin (MBSA). The whole process involved no synthesis of conductive nanomaterials or addition of initiators. Remarkably, the acquired superhydrophilic hydrogel exhibited a surprisingly favourable adhesion to the electrode surface, attributed to the carboxyl groups and related denser gel network resulting from the LM@SA nanoparticles. Finally, the prepared electrochemical immunosensor possessed excellent repeatability, storage stability, selectivity and meanwhile a wide linear range from 10 pg mL−1–100 ng mL−1, and an ultralow detection limit of 8.23 pg mL−1 for the detection of motilin even in 100 % human serum. Moreover, this was a successful attempt of LM-based nanocomposite hydrogel as an electrochemical sensing matrix, and we believe it could present further opportunities toward more satisfying sensing interface for biosensing and bioelectronics with more research in future.

Two-dimensional titanium carbide MXene embedded in exfoliated graphite nanoplatelets for voltammetric sensing of thiamethoxam in beekeeping products

To prepare a novel and highly sensitive electrochemical sensor for determination of Thiamethoxam (a neonicotinoid insecticide), a nanohybrid material was utilized based on two-dimensional titanium carbide (Ti3C2Tx), belonging to the MXenes class, and exfoliated graphite nanoplatelets. The resulting material was characterized with different techniques, such UV-Vis, XRD, SEM, TEM and XPS. The sensor displayed a remarkable improvement in current responses for the electrochemical reduction of thiamethoxam compared to the bare glassy carbon electrode. Under optimized conditions, a calibration curve was built by differential pulse voltammetry in the range of 0.048 to 30 µmol L−1 with limit of detection of 20 nmol L−1. Recovery data from 90 to 105% were obtained in beekeeping samples using the proposed sensor. Additionally, the sensor presented accurate and precise data when compared to chromatographic method data, and it was validated with statistical tests.

Empowering an Acute Kidney Injury 3D Graphene-Based Sensor Using Extreme Learning Machine.

This study reports on the application of an extreme learning machine (ELM) in near-real-time kidney monitoring via urine neutrophil gelatinase-associated lipocalin (NGAL) detection with a 3D graphene electrode. This integration marks the first instance of combining a graphene-based electrode with machine learning to enhance the NGAL detection accuracy, building on our group's 2020 research. The methodology involves two key components: a graphene electrode functionalized with a lipocalin-2 antibody for NGAL detection and the ELM application for improved prediction accuracy by using urine analysis data. The results show a significant 15% increase in the area under the curve (AUC) for NGAL determination, with error reduction from ±6 to 0.54 ng/mL within a linear range of 2.7-140 ng/mL. The ELM also lowered the detection limit from 14.8 to 0.89 ng/mL and increased accuracy, precision, sensitivity, specificity, and F1 score for AKI prediction by 8.89, 30.69, 6.78, 9.94, and 19.07%, respectively. These findings underscore the efficacy of simple neural networks in enhancing graphene-based electrochemical sensors for AKI biomarkers. ELM was chosen for its optimal performance-resource balance, with a comparative analysis of ELM, support vector machines, multilayer perceptron, and random forest algorithms also included. This research suggests the potential for miniaturizing AI-enhanced sensors for practical applications.

Innovative use of shrimp shell powder in carbon paste electrode for the electrochemical detection of dopamine and paracetamol: Valorization, characterization and application

The present study outlines the design of an innovative, cost-effective, and environmentally friendly electrochemical sensor, based on a carbon paste electrode (CPE) modified by shrimp shell waste (SSW). The developed electrode was used to facilitate the electrocatalytic detection of two compounds, namely dopamine (DA) and paracetamol (PAR). The use of SSW as an electrode material is ground breaking. The results have shown that the addition of shrimp shell (SS) in the CPE has led to a significant increase in the active surface area (0.504 cm2) and has improved electron transfer by decreasing the charge transfer resistance (17.45 Ω.cm2) at the electrode/solution interface. The SSW was characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffractometry (XRD), and fourier transform infra-red (FTIR). The results show a fibrous and porous structure with high calcium content and other chemical elements including carbon, oxygen, sulphur, phosphorus and nitrogen. The electrochemical behavior of DA and PAR on the CPE-SS electrode was studied using cyclic voltammetry (CV), chronoamperometry (CA), electrochemical impedance spectroscopy (EIS), and square wave voltammetry (SWV) techniques. Additionally, CPE and CPE-SS electrodes were examined by SEM/EDS and FTIR. The effect of scan rate shows that the electrochemical process is diffusion controlled for DA and PAR. The CPE-SS electrode provide a wide linear range, good selectivity, repeatability, precision (≤5%), and low detection limits 3.6 µM and 5.54 µM for DA and PAR, respectively. In addition, the developed sensor was applied to detect DA and PAR in urine, tap water, and pharmaceutical tablets with apparent recoveries.

Molecularly imprinted electrochemical sensor for ethyl carbamate detection in Baijiu based on “on-off” nanozyme-catalyzing process

Ethyl carbamate (EC) is a carcinogen widely found in the fermentation process of Baijiu. Herein, we construct a molecularly imprinted polymers/MXene/cobalt (II) based zeolitic imidazolate frameworks (MIP/MXene/ZIF-67) nano-enzyme sensor for the detection of EC during Baijiu production. The ZIF-67 is synthesized in situ on the MXene nanosheets to provide a superior catalytic activity to H2O2 and amplify the electrochemical signal. The MIP is prepared by the polymerization reaction to recognize EC. Owing to the interaction between EC and EC-MIP, the interferences are effectively eliminated, greatly improving the accuracy of the expected outcome. This approach attains an ultrasensitive assay of EC ranging from 8.9 μg/L to 44.5 mg/L with detection limit of 0.405 μg/L. The accuracy of this method is confirmed by the recovery experiment with good recoveries from 95.07% to 107.41%. This method is applied in natural EC analyses, and the results are consistent with certified gas chromatograph- mass spectrometer.