Simultaneous electrochemical sensing of heavy metal ions (Zn2+, Cd2+, Pb2+, and Hg2+) in food samples using a covalent organic framework/carbon black modified glassy carbon electrode.

In this study, for the first time, a selective electrochemical sensor by glassy carbon electrode (GCE) modified with the covalent organic framework (COF) and carbon black (CB) was introduced and applied to simultaneous sensing of Zn2+, Cd2+, Pb2+, and Hg2+ via differential pulse anodic stripping voltammetry (DPASV). The COF is supplied through a condensation reaction between melamine and trimesic acid. The COF and CB, which are used to modify the GCE surface, increase electrochemical activity. The linearity to determine ions was achieved as Zn2+: 0.009-1100 nM, Cd2+: 0.005-1100 nM, Pb2+: 0.003-1100 nM, and Hg2+: 0.001-1100 nM. Besides, the detection limits for Zn2+, Cd2+, Pb2+, and Hg2+ have obtained 0.003, 0.002, 0.001 and 0.0003 nM, respectively. The CB-COF/GCE was applied to simultaneously measure the ions in food samples. For validation, atomic absorption spectrometry (AAS) was applied to measure the amount of target metal ions as a standard method in real samples.

Aptasensor based on high surface area covalent organic framework for simple and ultrasensitive detection of sarcosine in the diagnosis of prostate cancer.

In this study, an electrochemical aptasensor was developed for the specific detection of sarcosine using a covalent organic framework (COF). The imine-based two-dimensional COF was synthesized through a solvothermal process using terephthaldehyde and melamine. This resulted in the formation of a structure that is highly porous and has a unique surface area of 908 m2/g. The produced biosensor demonstrated a significant linear relationship between charge transfer resistance (Rct) and various concentrations of sarcosine in blood serum samples. The aptasensor had two linear ranges, spanning from 0.5 fM to 700 fM and 10 pM to 0.12 nM, respectively, with a detection limit of 0.15 fM. The incorporation of high surface area COFs in the aptasensor design offers a promising combination of sensitivity, stability, and specificity. This combination creates a valuable device for diagnosing and monitoring of prostate cancer and potentially other diseases.

A dual functional turn off florescence sensor using metal-organic framework for sensitive detection of aluminum(III) in aqueous solution.

Aluminum, classified as one of the toxic heavy metals, has a recommended daily consumption limit of 3-10 mg, as specified by the World Health Organization (WHO). Herein, the selective and sensitive aluminum(III) fluorescence sensor based on TMU-16 metal-organic frameworks (MOFs) in aqueous medium, is reported. A sensing pathway was found via the cation exchange between aluminum(III) and zinc(II) ions, and caused selectivity and sensitivity detection of aluminum(III) with a 5-100 ppm linear range and 1.99 ppm limit of detection (LOD). This sensor offers the advantage of accurately determining the concentration range of aluminum(III) ions. At low concentrations, only fluorescence quenching was observed, while at higher concentrations, fluorescence emission not only undergoes quenching but also exhibits a blue shift in wavelength. Notably, the sensor demonstrates no interference from cation solutions of mercury(II), zinc(II), nickel(II), lead(II), cobalt(II), cadmium(II), silver(I), chromium(III), and iron(III). Another significant feature of this sensor is its selectivity toward copper(II) and aluminum(III) ions, due to quenching fluorescence in the presence of copper(II) ion. The results presented the sensor's selectivity toward copper(II) at low concentrations and aluminum(III) at high concentrations.

Electrochemical impedance biosensor based on Y chromosome-specific sequences for fetal sex determination.

A new electrochemical biosensor based on the sequence of chromosome Y (SRY) has been introduced to determine the gender of the fetus. At first, the DNA probe was designed based on the SRY gene sequence on chromosome Y. Then, a suitable functional group was added to the DNA probe, and it has been immobilized on the surface of the electrode modified with a nanocomposite containing Cu(OH)2 @N-C n-boxes. This substrate causes more DNA probes to connect to the electrode surface by increasing the effective surface area. The presence of the SRY sequence in the DNA sample extracted from blood was detected by the electrochemical signal of the bio-sensor. After optimizing the parameters, the fabricated genosensor showed linear responses in the two concentration ranges containing 0.5 fM to 50 pM and 50 pM to 500 nM. The limit of detection (LOD) for the proposed method was 0.16 fM. The proposed genosensor has been successfully used to determine the gender of the fetus using cell-free fetal DNA (cffDNA) in the blood plasma of several pregnant mothers. This method has advantages such as being simple, portable, accurate, and non-invasive for early determination of the gender of the fetus and early diagnosis of X-linked genetic disorders.

Fabrication of an electrochemical aptasensor for the determination of sarcosine based on synthesized CuCo2O4 nanosheets.

Sarcosine (SRN) detection in body fluids is related to the diagnosis of prostate cancer. However, the development of SRN biosensors has been limited due to the low concentration of SRN in body fluids. Here, a new electrochemical strategy for selective and accurate determination of SRN in urine samples is reported. CuCo2O4 nanosheets (CuCo2O4 NSs) have been synthesized and used as a new platform in the design of efficient electrochemical aptasensors for prostate cancer diagnosis. As far as we know, CuCo2O4 NSs have not been used so far in electrochemical aptasensor design. The presence of CuCo2O4 NSs on the electrode surface as a platform improves the conductivity and surface area. Therefore, it can be very effective in improving the diagnostic performance of the electrochemical aptasensor. The linear concentration range and limit of detection (LOD) for this strategy were calculated to be 1 pM- 8 µM and 350 fM, respectively.

Facile and innovative application of surfactant-modified-zeolite from Austrian fly ash for glyphosate removal from water solution.

This study highlights a pioneering approach in the development of an efficient, affordable, and economically feasible adsorbent specifically tailored for the removal of glyphosate (Gly) from contaminated water. To accomplish this objective, a low-cost and pure NaA Zeolite (NaAZ) was synthesized with 93% crystallinity from Austrian fly ash (AFA) as a precursor for the first-time. Taguchi design was employed to optimize critical parameters such as the SiO2/Al2O3 ratio, alkalinity concentration, time, and temperature. The cation exchange capacity (CEC) and external cation exchange capacity (ECEC) are determined as critical factors for the modification process. Subsequently, the pure NaAZ was modified with hexadecyl trimethyl ammonium chloride (HDTMAC), a cationic surfactant. The utilization of surfactant-modified zeolite (SMZ) for Gly removal demonstrates its innovative application in this field, highlighting its enhanced adsorption capacity and optimized surface properties. The AFA, NaAZ, and SMZ were characterized using analytical techniques including XRD, XRF, FTIR-ATR, SEM, TGA, BET, CHNSO analyzer and ICP-OES. The adsorbent exhibited effective Gly removal through its pH-dependent charge properties (pH 2-10), with an optimized pH 6 facilitating a significant electrostatic interaction between the adsorbent and Gly. SMZ demonstrated remarkable adsorption capacity and removal efficacy, surpassing most reported adsorbents with values of 769.23 mg/g and 98.92% respectively. Our study demonstrates the significant advantage of the SMZ, with a low leaching concentration of only 6 ppm after 60 days, ensuring environmental safety, long-term stability, and public health considerations. The kinetics of the adsorption process was well described by the pseudo-second order and the Freundlich isotherm. Pore diffusion and H-bonding were postulated to be involved in physisorption, whereas electrophilic interactions led to chemisorption type of adsorption. Consequently, SMZ provides a practical significance, broad applicability and promising solution for Gly removal, facilitating sustainable water treatment.

Electrochemical sensor based on molecularly imprinted copolymer for selective and simultaneous determination of riboflavin, dopamine, and L-tryptophan.

This research shows the exact detection of riboflavin (RF), dopamine (DA), and L-tryptophan (Trp) through molecularly imprinted polymer (MIP) based on the electropolymerization method. MIP was placed on the surface of the glassy carbon electrode (GCE) by electropolymerization of monomers such as catechol and para-aminophenol, in the presence of all three analytes. The introduced sensor was investigated using field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM), Fourier-transform infrared spectroscopy (FTIR), and electrochemical methods, for example, electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and differential pulse voltammetry (DPV). The MIP/GCE performs well in terms of selectivity, reproducibility, repeatability, and stability. This sensor revealed good linear ranges of 0.005-500 µM for RF, 0.05-500 µM for DA, and 0.1-250 µM for Trp with limits of detection (LOD) as 0.0016 µM, 0.016 µM, and 0.03 µM for RF, DA, and Trp, respectively. The modified GCE was successfully applied to detect RF, DA, and Trp in serum and milk samples with satisfactory results.

Solar energy-based electromembrane extraction using agarose gel for the determination of nonsteroidal anti-inflammatory drugs from biological samples: An environmentally friendly strategy.

This paper presents the application of solar energy as a renewable resource in gel electromembrane extraction (G-EME). The extraction driving force (electrical field) generated from solar energy is stored through photovoltaic panels and significantly contributes to reducing the emission of greenhouse gasses. Moreover, the replacement of the polypropylene membrane and organic extracting solvents with biodegradable agarose membrane and the aqueous extracting solutions makes the presented approach compatible with the principles of green chemistry. Naproxen (NAP) and ibuprofen (IBF) were extracted from urine samples to the aqueous acceptor phase containing an anode electrode situated on the other side of the agarose gel membrane. Acceptable linearity was obtained in the concentration ranges of 6-100 and 9-100 µg. L - 1 with detection limits of 2 and 3 µg. L - 1 for NAP and IBF, respectively.

Flower-like core-shell nanostructures based on natural asphalt coated with Ni-LDH nanosheets as an electrochemical platform for prostate cancer biomarker sensing.

Flower-like core-shell nanostructures based on natural asphalt (NA) coated with nickel-layered double hydroxide nanosheets (Ni-LDH NSs) were synthesized for the first time. The synthetic nanostructures were successfully used as an efficient platform in the design of sarcosine (SAR) electrochemical aptasensor. SAR is considered an efficient biomarker for prostate cancer (PCa) diagnosis. However, the low concentration of SAR in urine, plasma, and tissue cells has limited the growth of SAR biosensors. The performance of the presented SAR aptasensor is very promising in being applied as a portable device in the identification of PCa. After drawing the calibration curve, the linear concentration range was obtained in two ranges from 5 pM to 100 nM and 100 nM to 7.9 µM, and the limit of detection (LOD) was calculated to be 1.6 pM. This study can provide a basis for wider research in various programs such as developing PCa diagnostic aptasensors and investigating the use of NA nanostructures in other electrochemical applications such as electrocatalysis and energy storage.

Selective determination of cadmium and lead ions in different food samples by poly (riboflavin)/carbon black-modified glassy carbon electrode.

In this research, a poly (riboflavin)/carbon black-modified glassy carbon electrode (PRF/CB/GCE) is introduced as a novel electrochemical sensor toward Cd2+ and Pb2+ simultaneous measurement in presence of bismuth ions, applying differential pulse anodic stripping voltammetry (DPASV). Regarding the optimized conditions, the linear ranges were achieved from 0.5 to 600 nM for Cd2+ and Pb2+. The detection limit (LOD) was found to be 0.16 nM for Cd2+ and 0.13 nM for Pb2+. In order to perform the technique in real application, the proposed electrode was used to simultaneously detect ions in rice, honey, and vegetable samples with satisfactory recoveries - indicating that the sensor possesses good practicability to determine Cd2+ and Pb2+. Moreover, an atomic absorption spectrometry (AAS) was used in order to detect the concentration of ions as a reference technique in rice, honey, and vegetable samples.

Three-dimensional modeling of streptomycin binding single-stranded DNA for aptamer-based biosensors, a molecular dynamics simulation approach.

Streptomycin (STR) an aminoglycoside antibiotic which is used against bacteria in human and animal infection, have serious side effects on different parts of human body. Therefore, there is a crucial need to detect trace amount of it in serum and food products. Aptamers are oligonucleotides or peptides, which bind their targets with high affinity and specificity. These properties make aptamers as suitable candidates for biosensing applications. A 79-mer ss-DNA aptamer was applied for the detection of small amount of STR in various aptasensors. But there is no structural information on the STR-binding aptamer and molecular details underlying the aptamer-STR binding remain unexplored. In this study we provided a 3D-structural model for 79-mer ss-DNA aptamer from the sequence. Using docking program and molecular dynamics (MD) simulation we predicted the binding pocket of ss-DNA aptamer. Our results show STR streptose ring is buried within the groove of DNA model and capped by non Watson-Crick bases. STR interacts with aptamer through forming stable hydrogen bonds. Our computational findings are in fair agreement with experimental results. With the atomic structural details, we gained new insight into the Apt-STR binding interaction that can help to further optimize aptamer efficiency in biosensing applications.Communicated by Ramaswamy H. Sarma.

Electronic tongue as innovative instrument for detection of crocin concentration in saffron (Crocus sativus L.).

Electronic tongue is a new approach for simple and fast detection, classification, and quantification of the solved compounds. Crocin is the main source of color of saffron (Crocus sativus L.). An electronic tongue system was used to predict the concentration of saffron crocin in the present study. The measurement system included an electrochemical sensor array based on voltammetry electrodes, a three-electrode cell, a potentiostat, a personal computer. Aqueous analyte were provided by blending pure crocin and different saffron samples from Iran and Spain with distilled water. Output signals of the electronic tongue system were analyzed by principal component analysis and artificial neural networks. Based on principal component analysis, the total variance among pure crocin was 99% and that of saffron samples was 100%. The accuracy of artificial neural network model was 98.80%. The results indicated that the developed electronic tongue system and artificial neural network model can successfully predict crocin concentration in saffron.

SARS-CoV-2 virus label-free electrochemical nanohybrid MIP-aptasensor based on Ni3(BTC)2 MOF as a high-performance surface substrate.

A dual recognition biosensor was developed via introducing aptamer strings and molecular imprinting polymer (MIP) for the selective detection of intact SARS-CoV-2 virus based on screen printed carbon electrode (SPCE) modified with nickel-benzene tricarboxylic acid-metal-organic framework (Ni3(BTC)2 MOF) synthesized by in situ growth method, SARS-CoV-2 S protein-specific amino-aptamer and electropolymerization of dopamine (ePDA). The proposed biosensor showed an excellent linear relationship between charge transfer resistance (Rct) and increase in virus concentration in the range 10 to 108 plaque-forming units/mL (PFU/mL) with a low detection limit of 3.3 ± 0.04 PFU/mL and response time of 20 min. Compared with single-element sensors (aptamer or MIP), it showed higher selectivity for  the SARS-CoV-2 virus and facilitated detection in real samples.

A new method for electrochemical determination of Hippuric acid based on molecularly imprinted copolymer.

This study introduces easy detection of Hippuric Acid (HA) through electrochemical polymerization technique. The molecularly imprinted polymer (MIP) was immobilized on a glassy carbon electrode (GCE) through electropolymerization of monomers, including m-dihydroxy benzene (m-DB) and o-aminophenol (o-AP), in presence of HA as the template. Moreover, it was subsequently delineated using electrochemical probe of hexacyanoferrate redox, atomic force microscopy (AFM), fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and electrochemical techniques such as cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS). This sensor exhibited limit of detection (0.012 nM) with a good linear range of 0.05-40 nM and 40-500 nM. The developed sensor was properly employed to determine HA in real samples with acceptable results.

Label-free electrochemical aptasensor for rapid detection of SARS-CoV-2 spike glycoprotein based on the composite of Cu(OH)2 nanorods arrays as a high-performance surface substrate.

The development of advanced electrode materials and the combination of aptamer with them have improved dramatically the performance of aptasensors. Herein, a new architecture based on copper hydroxide nanorods (Cu(OH)2 NRs) are directly grown on the surface of screen printed carbon electrode (SPCE) using a two-step in situ, very simple and fast strategy and was used as a high-performance substrate for immobilization of aptamer strings, as well as an electrochemical probe to development a label-free electrochemical aptasensor for SARS-CoV-2 spike glycoprotein measurement. The Cu(OH)2 NRs was characterized using X-ray Diffraction (XRD) and electron microscopy (FESEM). In the presence of SARS-CoV-2 spike glycoprotein, a decrease in Cu(OH)2 NRs-associated peak current was observed that can be owing to the target-aptamer complexes formation and thus blocking the electron transfer of Cu(OH)2 NRs on the surface of electrode. This strategy exhibited wide dynamic range in of 0.1 fg mL-1 to 1.2 µg mL-1 and with a high sensitivity of 1974.43 µA mM-1 cm-2 and low detection limit of 0.03 ± 0.01 fg mL-1 of SARS-CoV-2 spike glycoprotein deprived of any cross-reactivity in the presence of possible interference species. In addition, the good reproducibility, repeatability, high stability and excellent feasibility in real samples of saliva and viral transport medium (VTM) were found from the provided aptasensor. Also, the aptasensor efficiency was evaluated by real samples of sick and healthy individuals and compared with the standard polymerase chain reaction (PCR) method and acceptable results were observed.

Hierarchical nickel hydroxide nanosheets grown on hollow nitrogen doped carbon nanoboxes as a high-performance surface substrate for alpha-fetoprotein cancer biomarkers electrochemical aptasensing.

During recent decades, we have witnessed a great improvement in the performance of aptamer-based sensors, specifically when aptamers are combined with new nanomaterials; as a platform for biosensors. The design of hollow carbon-based materials has also received a lot of attention due to its excellent properties in various applications. Herein, we aim at designing hierarchical porous Ni(OH)2 nanosheets on hollow N-doped carbon nanoboxes Ni(OH)2@N-C n-box). In this sense, we obtained the hollow N-C n-box skeletons from the Fe2O3 nanocubes template. The development of label-free electrochemical aptasensor was carried out using the covalently immobilizing NH2-functionalized aptamer on Ni(OH)2@N-C n-box as an efficient substrate. The Ni(OH)2@N-C n-box was characterized using scanning fourier transform infrared spectroscopy (FTIR), X-ray Diffraction (XRD), Brunauer, Emmett and Teller (BET), transmission electron microscopes (TEM) and electron microscopy (FESEM). The electrochemical evaluations clarified the fact that a linear relationship exists between the alpha-fetoprotein (AFP) contents and the charge transfer resistance (Rct) (from 1 fg mL-1 to 100 ng mL-1) with a low detection limit of 0.3 fg mL-1. Moreover, regarding the aptasensor, the superior detection recoveries were experienced in real biological samples, illustrating its great detection performance and practical feasibility. Considering the aptasensor application, these studies showed that Ni(OH)2@N-C n-box possesses different enhanced electrochemical features, making it appropriate as an electrode material for aptasensor application.

A novel electrochemical sensor for the determination of histidine based on a molecularly imprinted copolymer.

The present study aimed to report a novel electrochemical sensor through electropolymerization of o-aminophenol (o-AP) and m-dihydroxy benzene (m-DB) as monomers on the surface of the glassy carbon electrode (GCE) for the determination of histidine (His) as a template molecule. The developed sensor exhibited satisfactory sensitivity and high selectivity, and also offered a linear range between 0.005 and 10.0 µM with a detection limit of 0.9 nM. Finally, it is worth mentioning that we also aimed at employing the proposed sensor for the detection of His in blood serum samples.

An electrochemical immunosensor using SARS-CoV-2 spike protein-nickel hydroxide nanoparticles bio-conjugate modified SPCE for ultrasensitive detection of SARS-CoV-2 antibodies.

As a promising approach for serological tests, the present study aimed at designing a robust electrochemical biosensor for selective and quantitative analysis of SARS-CoV-2-specific viral antibodies. In our proposed strategy, recombinant SARS-CoV-2 spike protein antigen (spike protein) was used as a specific receptor to detect SARS-CoV-2-specific viral antibodies. In this sense, with a layer of nickel hydroxide nanoparticles (Ni(OH)2 NPs), the screen-printed carbon electrode (SPCE) surface was directly electrodeposited to ensure better loading of spike protein on the surface of SPCE. The differential pulse voltammetry (DPV) showed signals which were inversely proportional to the concentrations of the antibody (from 1 fg mL-1 L to 1 µg mL-1) via a specific and stable binding reaction. The assay was performed in 20 min with a low detection limit of 0.3 fg mL-1. This biodevice had high sensitivity and specificity as compared to non-specific antibodies. Moreover, it can be regarded as a highly sensitive immunological diagnostic method for SARS-CoV-2 antibody in which no labeling is required. The fabricated hand-held biodevice showed an average satisfactory recovery rate of ~99-103% for the determination of antibodies in real blood serum samples with the possibility of being widely used in individual serological qualitative monitoring. Also, the biodevice was tested using real patients and healthy people samples, where the results are already confirmed using the enzyme-linked immunosorbent assay (ELISA) procedure, and showed satisfactory results.

Electrochemical immunosensor with Cu2O nanocube coating for detection of SARS-CoV-2 spike protein.

Severe acute respiratory syndrome SARS-CoV-2 has caused a global pandemic starting in 2020. Accordingly, testing is crucial for mitigating the economic and public health effects. In order to facilitate point-of-care diagnosis, this study aims at presenting a label-free electrochemical biosensor as a powerful nanobiodevice for SARS-CoV-2 spike protein detection. Utilizing the IgG anti-SARS-CoV-2 spike antibody onto the electrode surface as a specific platform in an ordered orientation through staphylococcal protein A (ProtA) is highly significant in fabricating the designed nanobiodevice. In this sense, the screen-printed carbon electrode modified with Cu2O nanocubes (Cu2O NCs), which provide a large surface area in a very small space, was applied in order to increase the ProtA loading on the electrode surface. Accordingly, the sensitivity and stability of the sensing platform significantly increased. The electrochemical evaluations proved that there is a very good linear relationship between the charge transfer resistance (Rct) and spike protein contents via a specific binding reaction in the range 0.25 fg mL-1 to 1 µg mL-1. Moreover, the assay when tested with influenza viruses 1 and 2 was performed in 20 min with a low detection limit of 0.04 fg mL-1 for spike protein without any cross-reactivity. The designed nanobiodevice exhibited an average satisfactory recovery rate of ~ 97-103% in different artificial sample matrices, i.e., saliva, artificial nasal, and universal transport medium (UTM), illustrating its high detection performance and practicability. The nanobiodevice was also tested using real patients and healthy samples, where the results had been already obtained using the standard polymerase chain reaction (PCR) procedure, and showed satisfactory results. Graphical abstract.

Fabrication of an electrochemical biodevice for ractopamine detection under a strategy of a double recognition of the aptamer/molecular imprinting polymer.

The importance of RAC tracking in human biofluids has boosted many demands for designing an ultrasensitive tool to determine the trace value of the RAC from clinical, judicial, and forensic centers. In this study, an electrochemical biodevice has developed for the highly selective detection of this illegal feed additive under a double recognition strategy of the aptamer (Apt) and molecular imprinting polymer (MIP) on a glassy carbon electrode (GCE). The sensing relies on this fact that both the MIP and Apt act synergistically to trap the RAC molecules. The sensing surface fabrication steps have been monitored by some electrochemical techniques such as electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV(. The charge transfer resistance (Rct) value of the redox probe as a representative of the biodevice response has increased linearly with the RAC concentration increasing in a dynamic range of 1 fM to 1.90 µM. The detection limit (LOD) value has been estimated to be 330 aM, lower than all of the reported methods in the RAC sensing. Furthermore, the practical feasibility of biodevice has been evaluated in some human blood serum and urine samples. This strategy offers some useful advantages in reliable detection of the RAC, which may help in the routine analysis, as mandated by regulatory agencies.