Biosensor based on atemoya peroxidase immobilised on modified nanoclay for glyphosate biomonitoring (original) (raw)
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Electrochemical Nanobiosensor for Glyphosate Herbicide and Its Metabolite
Electroanalysis, 2009
The use of amperometric biosensor for the detection of glyphosate herbicide and its metabolite aminomethylphosphonic acid (AMPA) is presented. The biosensor was developed by electrochemically depositing poly(2,5dimethoxyaniline) (PDMA) doped with poly(4-styrenesulfonic acid) (PSS) onto the surface of a gold electrode followed by electrostatic attachment of horseradish peroxidase (HRP) onto the PDMA-PSS nanocomposite film. The PDMA-PSS film was characterized by transmission electron microscopy (TEM) and Fourier Transform infrared (FTIR) spectroscopy. The HRP immobilized on the PDMA-PSS film catalyzed the reduction of hydrogen peroxide, the inhibition of which was applied in the detection of glyphosate and AMPA. The limits of detection of the biosensor for glyphosate and AMPA were 0.16 mg L À1 and 1.0 mg L À1 , respectively. The study demonstrates that the biosensor is very sensitive and could be a useful tool in the screening of glyphosate and AMPA at low concentrations.
Microchemical Journal, 2021
Glyphosate is the most widely used herbicide in Argentina. The information about this herbicide is controversial as some organisms classify it as dangerous and others as safety. Moreover, the world regulations are very different depending on country. However, many studies had reported its presence in numerous sample types, and also, had demonstrated adverse effects on environmental and human health. In the present work, two electrochemical screening methods based on horseradish peroxidase (HRP) inhibition have been developed for the glyphosate detection. In one of them, the working electrode was built in our laboratory with a graphite-epoxy compound mixture (GEC-E). While the other is based on a biosensor built with commercial screen-printed electrodes (SPE), for which on the working electrode, the HRP enzyme was immobilized by using the affinity reaction between streptavidin and biotin-peroxidase. The detection electrochemical technique was square-wave voltammetry (SWV). When glyphosate inhibits the activity of the soluble or immobilized enzyme, a decrease in the signal is generated at the electrode or biosensor, respectively, and this decrease is proportional to the amount of glyphosate in the sample. The linear range obtained was from 0.16 to 500 ng L-1 glyphosate (R 2 = 0.9727) for the soluble HRP-based inhibition method with a limit of detection (LOD) of 0.085 ng L-1. While the range was from 0.08 to 11 μg L-1 glyphosate (R 2 = 0.9799) for immobilized HRP-based inhibition method with a LOD of 45 ng L-1. For the screening detection of glyphosate, the decision limits (CCα) and detection capabilities (CCβ) were 115 and 130 ng L-1 for the soluble HRP-based inhibition method and 111 and 122 ng L-1 for biosensor, respectively. Recoveries from 71% to 96% and from 79% to 120% were obtained by two electrochemical methods from groundwater and superficial water with high organic matters spiked with glyphosate, respectively. Therefore, both electrochemical methods allow determining the glyphosate concentration at trace levels in accordance with the strictest European Parliament regulation (100 ng L-1). The soluble HRP-based inhibition method shown better performance than biosensor, but the latter due to its simplicity, stability and portability could be used in the field monitoring or detection of this herbicide in the exposed areas.
Nanomaterial-Based Sensors for the Detection of Glyphosate
Water, 2022
Due to its chemical properties, glyphosate [N-(phosphonomethyl)glycine] is one of the most commonly used agricultural herbicides globally. Due to risks associated with human exposure to glyphosate and its potential harmfulness, the need to develop specific, accurate, online, and sensitive methods is imperative. In accordance with this, the present review is focused on recent advances in developing nanomaterial-based sensors for glyphosate detection. Reported data from the literature concerning glyphosate detection in the different matrices using analytical methods (mostly chromatographic techniques) are presented; however, they are expensive and time-consuming. In this sense, nanosensors’ potential applications are explained to establish their advantages over traditional glyphosate detection methods. Zero-dimensional (0D), one-dimensional (1D), two-dimensional (2D), and three- dimensional (3D) materials are reviewed, from biomolecules to metallic compounds. Bionanomaterials have generated research interest due to their selectivity with respect to using enzymes, DNA, or antibodies. On the other hand, Quantum Dots also are becoming relevant for their vast surface area and good limit of detection values (in the range of pM). This review presents all the characteristics and potential applications of different nanomaterials for sensor development, bearing in mind the necessity of a glyphosate detection method with high sensitivity, selectivity, and portability. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY
Recent Advances in Non-Enzymatic Electrochemical Sensors for Glyphosate Detection: A Review
Glyphosate (GLY) is the most widely used organophosphorus pesticides globally with application in shielding crops against perennial and annual the weeds, domestic garden and agriculture. It is recognized for its toxicological harm and is implicated in potential connections with human carcinogenesis. Generally, glyphosate is considered to be less toxic but excessive use leads to pollute soil, food and water. Furthermore, it strongly effects the unicellular and multicellular organism. Therefore, there is urgent need to develop specific, accurate, online, and sensitive methods for detection of glyphosate. The present review is focused on recent advances in developing non-enzymatic sensors for glyphosate detection. Non-enzymatic electrochemical sensors have emerged as promising alternatives for glyphosate detection, offering advantages such as high sensitivity, selectivity, and rapid response. The electrodes were modified with metals, carbon materials, metal organic framework and molecular imprinted polymers using various electrochemical techniques. Execution, benefits, linear range, detection limit and limitations of the modified sensors for determination of glyphosate are reviewed thoroughly.
Pure and Applied Chemistry, 2000
This study presents a simple, sensitive, rapid, and low-cost amperometric method for direct and quantitative determination of glyphosate and glufosinate herbicides. Electrochemical synthesis and characterization of poly(2,5-dimethoxyaniline)-poly(4styrenesulfonic acid) (PDMA-PSS) nanoparticles was achieved by cyclic voltammetry (CV) and scanning electron microscopy (SEM). The nanobiosensor was constructed by immobilizing the enzyme horseradish peroxidase (HRP) electrostatically onto the surface of a rotating gold disk electrode modified with PDMA-PSS nanoparticles. The biosensing principle was based on determination of the sensor response to glyphosate and glufosinate by amperometric methods. Hydrogen peroxide (H 2 O 2 ) was used to measure activity of the enzyme before injection of the herbicides into the electrolyte solution. The enzyme electrode was stable for a long period of time and was used for over 60 measurements. Glyphosate and glufosinate analyses were realized on spiked corn samples within a concentration range of 2.0-78.0 µg L -1 , corroborating that the nanobiosensor is sensitive enough to detect herbicides in these matrices. Based on a 20-µL sample injection volume, the detection limits were 0.1 µg L -1 (10 -10 M) for both glyphosate and glufosinate without sample clean-up or preconcentration.
Electrochemical Biosensor for Sensitive Quantification of Glyphosate in Maize Kernels
Electroanalysis, 2019
A graphite-epoxy electrode (GE) modified with multiwalled carbon nanotubes (MWCNTs) and horseradish peroxidase (GE/MWCNTs-HRP) was used to build a glyphosate biosensor whose performance in aqueous solutions depends on the enzyme activity. For the biosensor preparation, MWCNTs were deposited onto the GE surface by electrophoresis using an oxidative treatment (H 2 SO 4 /HNO 3) in presence of cetyl tributylammonium bromide (CTAB) as a cationic surfactant. The surfactant was further removed from the MWCNTs surface by dipping the electrode in an EtOH/HCl solution. The physical immobilization of HRP and therefore the glyphosate sensing capabilities was tested at pH 4 where the herbicide exhibits one only species. Circular dichroism studies suggested that the secondary structure of HRP changes as a result of its interaction with glyphosate and that this change is intensified by the combination of glyphosate and H 2 O 2 , which may explain the decrease of the enzyme catalytic activity with the increase of glyphosate concentration. The glyphosate quantification in doped-maize kernels was highly reproducible and exhibits detection and quantification limits of 1.32 pM and 1.63 pM respectively. The biosensor is also characterized by a high recovery (100 %) and precision (coefficient of variation < 1 %) and can be employed in presence of interfering substances such as chlorpyrifos (an organophosphate pesticide) and starch.
Journal of Materials Science: Materials in Electronics, 2020
A silicon/polyaniline/horseradish peroxidase enzyme (n-Si/PANI/HRP) electrode was obtained by potentiostatic electrodeposition processes. PANI thin films were electropolymerized on a silicon substrate at different electric potentials, and an HRP enzyme was electrodeposited on the best PANI thin film. The best PANI thin film was obtained under electrodeposition conditions of + 1.00 V (vs. Ag/AgCl) and 900 s, and the immobilization of the HRP enzyme was performed at an electric potential of − 0.50 V (vs. Ag/AgCl). The n-Si/PANI-and n-Si/PANI/HRP electrodes were characterized using scanning electron microscopy and atomic force microscopy. The detection capacity of the glyphosate of the n-Si/PANI/HRP electrode with the best morphological characteristics was evaluated according to the electric current density responses from the oxidation of hydroquinone molecules in a solution containing different concentrations of glyphosate. The detection was performed because of the inhibition of the HRP enzyme activity by the glyphosate molecules in the solutions with a lower concentration limit of 5.44 μg L −1 over an electric potential range of + 0.65 to + 1.15 V (vs. Ag/AgCl).