Electrochemical assisted enhanced nanozymatic activity of functionalized borophene for H2O2 and tetracycline detection

Syed Rahin Ahmed; Masoomeh Sherazee; Poushali Das; Md Shalauddin; Shamima Akhter; Wan Jeffrey Basirun; Seshasai Srinivasan; Amin Reza Rajabzadeh

doi:10.1016/j.bios.2023.115857

Electrochemical assisted enhanced nanozymatic activity of functionalized borophene for H₂O₂ and tetracycline detection

Syed Rahin Ahmed, Masoomeh Sherazee, Poushali Das, Md Shalauddin, Shamima Akhter, Wan Jeffrey Basirun, Seshasai Srinivasan, Amin Reza Rajabzadeh

Research output: Contribution to journal › Article › peer-review

18 Scopus citations

Abstract

This study unveils the electrochemically-enhanced nanozymatic activity exhibited by borophene during the reaction of 3,3′,5,5′-tetramethylbenzidine (TMB) and H₂O₂. Herein, the surface of the pristine borophene was first modified with the addition of thiocyanate groups to improve hydroxyl radical (•OH) scavenging activity. Then, the oxidation reaction of TMB was accelerated under applied electrochemical potential. Both factors significantly improved the detection limit and drastically decreased the detection time. DPPH testing revealed that the radical scavenging nature of borophene was more than 70%, boosting its catalytic activity. In the presence of H₂O₂, borophene catalyzed the oxidation of TMB and produced a blue-colored solution that was linearly correlated with the concentration of H₂O₂ and allowed for the detection of H₂O₂ up to 38 nM. The present finding was further extended to nanozymatic detection of tetracyclines (TCs) using a target-specific aptamer, and the results were colorimetrically quantifiable up to 1 μM with a LOD value of 150 nM. Moreover, transferring the principles of the discussed detection method to form a portable and disposable paper-based system enabled the quantification of TCs up to 0.2 μM. All the sensing experiments in this study indicate that the nanozymatic activity of borophene has significantly improved under electrochemical potential compared to conventional nanozyme-based colorimetric detection. Hence, the present discovery of electrochemically-enhanced nanozymatic activity would be promising for various sensitive and time-dependent colorimetric sensor development initiatives in the future.

Original language	English
Article number	115857
Journal	Biosensors and Bioelectronics
Volume	246
DOIs	https://doi.org/10.1016/j.bios.2023.115857
State	Published - 15 Feb 2024
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2023 Elsevier B.V.

Funding

Oxygen evolution reaction (OER) of bare GCE, borophene/GCE, and SCN-borophene/GCE was performed to investigate the catalytic effect by plotting the linear sweep voltammetry (LSV) polarization curve in 0.1 M KOH in the potential range of 0.2–0.9 V at 5 mVs−1. Fig. 2C shows the OER of (a) bare GCE, (b) borophene/GCE and (c) SCN-borophene/GCE with the results revealing that bare GCE shows the lowest current, which is attributed to slow charge transfer (Akhter et al., 2022). However, borophene/GCE exhibited a comparatively larger polarization curve than bare GCE, demonstrating a better electrocatalytic effect attributed to the presence of borophene on the GCE surface. However, SCN-borophene/GCE exhibited the largest polarization curve compared to the bare GCE and borophene/GCE, confirming the highest electrocatalytic activity. The presence of SCN enhances the kinetic reaction mechanism of the electrode. Fig. 2D (curve a) shows that the bare GCE possesses a Tafel slope with highest value of 45.25 mV/dec, while borophene/GCE shows lower slope of 16.75 mV/dec compared to the bare GCE. However, the SCN-borophene/GCE shows the lowest slope of 9.45 mV/dec, indicating that the SCN-borophene/GCE demonstrates a very fast OER. Here, the pristine BPH was a p-type semiconductor material. Once the negative charge SCNˉ group is attached to the p-type semiconductor phase of the BPH, a p-n heterojunction system is formed, which possesses higher conductivity and facilitates the OER significantly. In this study, the OER result is strongly supported by CV and EIS studies reaffirming that the SCN-borophene/GCE possesses the lowest Rct, highest conductivity and outstanding catalytic activity and electrochemical performance.The authors would like to acknowledge the support from the Natural Sciences and Engineering Research Council of Canada through their Discovery Grants (RGPIN-2019-07246 and RGPIN-2015-04737) and PPSI-2020-CLUSTER-IDIG04, from University of Malaya, Malaysia. The authors would like to acknowledge the support from the Natural Sciences and Engineering Research Council of Canada through their Discovery Grants ( RGPIN-2019-07246 and RGPIN-2015-04737 ) and PPSI-2020-CLUSTER-IDIG04 , from University of Malaya, Malaysia .

Funders	Funder number
SCN-borophene/GCE demonstrates a very fast OER
Natural Sciences and Engineering Research Council of Canada	RGPIN-2015-04737, PPSI-2020-CLUSTER-IDIG04, RGPIN-2019-07246
Universiti Malaya

Keywords

Borophene
Colorimetric detection
HO
Nanozyme
Paper-based assay
Tetracyclines

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10.1016/j.bios.2023.115857

Cite this

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title = "Electrochemical assisted enhanced nanozymatic activity of functionalized borophene for H2O2 and tetracycline detection",

abstract = "This study unveils the electrochemically-enhanced nanozymatic activity exhibited by borophene during the reaction of 3,3′,5,5′-tetramethylbenzidine (TMB) and H2O2. Herein, the surface of the pristine borophene was first modified with the addition of thiocyanate groups to improve hydroxyl radical (•OH) scavenging activity. Then, the oxidation reaction of TMB was accelerated under applied electrochemical potential. Both factors significantly improved the detection limit and drastically decreased the detection time. DPPH testing revealed that the radical scavenging nature of borophene was more than 70%, boosting its catalytic activity. In the presence of H2O2, borophene catalyzed the oxidation of TMB and produced a blue-colored solution that was linearly correlated with the concentration of H2O2 and allowed for the detection of H2O2 up to 38 nM. The present finding was further extended to nanozymatic detection of tetracyclines (TCs) using a target-specific aptamer, and the results were colorimetrically quantifiable up to 1 μM with a LOD value of 150 nM. Moreover, transferring the principles of the discussed detection method to form a portable and disposable paper-based system enabled the quantification of TCs up to 0.2 μM. All the sensing experiments in this study indicate that the nanozymatic activity of borophene has significantly improved under electrochemical potential compared to conventional nanozyme-based colorimetric detection. Hence, the present discovery of electrochemically-enhanced nanozymatic activity would be promising for various sensitive and time-dependent colorimetric sensor development initiatives in the future.",

keywords = "Borophene, Colorimetric detection, HO, Nanozyme, Paper-based assay, Tetracyclines",

author = "Ahmed, {Syed Rahin} and Masoomeh Sherazee and Poushali Das and Md Shalauddin and Shamima Akhter and Basirun, {Wan Jeffrey} and Seshasai Srinivasan and Rajabzadeh, {Amin Reza}",

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year = "2024",

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day = "15",

doi = "10.1016/j.bios.2023.115857",

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T1 - Electrochemical assisted enhanced nanozymatic activity of functionalized borophene for H2O2 and tetracycline detection

AU - Ahmed, Syed Rahin

AU - Sherazee, Masoomeh

AU - Das, Poushali

AU - Shalauddin, Md

AU - Akhter, Shamima

AU - Basirun, Wan Jeffrey

AU - Srinivasan, Seshasai

AU - Rajabzadeh, Amin Reza

PY - 2024/2/15

Y1 - 2024/2/15

N2 - This study unveils the electrochemically-enhanced nanozymatic activity exhibited by borophene during the reaction of 3,3′,5,5′-tetramethylbenzidine (TMB) and H2O2. Herein, the surface of the pristine borophene was first modified with the addition of thiocyanate groups to improve hydroxyl radical (•OH) scavenging activity. Then, the oxidation reaction of TMB was accelerated under applied electrochemical potential. Both factors significantly improved the detection limit and drastically decreased the detection time. DPPH testing revealed that the radical scavenging nature of borophene was more than 70%, boosting its catalytic activity. In the presence of H2O2, borophene catalyzed the oxidation of TMB and produced a blue-colored solution that was linearly correlated with the concentration of H2O2 and allowed for the detection of H2O2 up to 38 nM. The present finding was further extended to nanozymatic detection of tetracyclines (TCs) using a target-specific aptamer, and the results were colorimetrically quantifiable up to 1 μM with a LOD value of 150 nM. Moreover, transferring the principles of the discussed detection method to form a portable and disposable paper-based system enabled the quantification of TCs up to 0.2 μM. All the sensing experiments in this study indicate that the nanozymatic activity of borophene has significantly improved under electrochemical potential compared to conventional nanozyme-based colorimetric detection. Hence, the present discovery of electrochemically-enhanced nanozymatic activity would be promising for various sensitive and time-dependent colorimetric sensor development initiatives in the future.

AB - This study unveils the electrochemically-enhanced nanozymatic activity exhibited by borophene during the reaction of 3,3′,5,5′-tetramethylbenzidine (TMB) and H2O2. Herein, the surface of the pristine borophene was first modified with the addition of thiocyanate groups to improve hydroxyl radical (•OH) scavenging activity. Then, the oxidation reaction of TMB was accelerated under applied electrochemical potential. Both factors significantly improved the detection limit and drastically decreased the detection time. DPPH testing revealed that the radical scavenging nature of borophene was more than 70%, boosting its catalytic activity. In the presence of H2O2, borophene catalyzed the oxidation of TMB and produced a blue-colored solution that was linearly correlated with the concentration of H2O2 and allowed for the detection of H2O2 up to 38 nM. The present finding was further extended to nanozymatic detection of tetracyclines (TCs) using a target-specific aptamer, and the results were colorimetrically quantifiable up to 1 μM with a LOD value of 150 nM. Moreover, transferring the principles of the discussed detection method to form a portable and disposable paper-based system enabled the quantification of TCs up to 0.2 μM. All the sensing experiments in this study indicate that the nanozymatic activity of borophene has significantly improved under electrochemical potential compared to conventional nanozyme-based colorimetric detection. Hence, the present discovery of electrochemically-enhanced nanozymatic activity would be promising for various sensitive and time-dependent colorimetric sensor development initiatives in the future.

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KW - Colorimetric detection

KW - HO

KW - Nanozyme

KW - Paper-based assay

KW - Tetracyclines

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