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Altering the substituents of salicylic acid to improve Berthelot reaction for ultrasensitive colorimetric detection of ammonium and atmospheric ammonia

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Abstract

The Berthelot reaction is a classic method for detection of ammonium (NH4+) and atmospheric ammonia (NH3) by using salicylic acid (SA) as the chromogenic substrate. However, there lacks a method for improving the activity of the Berthelot reaction to enhance the analytical performance for detection of NH4+ and NH3. Here, five SA analogues with electron-withdrawing groups (-F) and electron-donating groups (-CH3 and -OCH3) at different positions of the aromatic ring have been chosen as the alternative to SA for Berthelot reaction. Among these analogues, 4-methoxysalicylic acid (4-OCH3-SA) shows the best colorimetric response and color change at a NH4+ concentration of 30 μM, and the sensitivity of 4-OCH3-SA-based colorimetric assay for NH4+ increases 1.75-fold compared with that of SA-based colorimetric method. This enhancement effect is attributed to the strong electron-donating property of 4-OCH3 group, activating the two-step electrophilic aromatic substitution reaction in the Berthelot reaction. Additionally, visual and sensitive detection of NH3 is realized, along with a low limit of detection down to 0.037 ppm. Furthermore, we demonstrate that this assay is reliable and practical for detection of NH4+ and NH3 in real water and air samples with good accuracy.

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Funding

We received financial support of the National Natural Science Foundation of China (41831285).

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Author notes

  1. Haili Yu and Guihua Zhang contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory of Solid Waste Treatment and Resource Recycle, Ministry of Education, Southwest University of Science and Technology, Mianyang, 621010, People’s Republic of China

    Haili Yu, Guihua Zhang & Faqin Dong

  2. Chongqing Key Laboratory of Environmental Materials and Remediation Technology, Chongqing University of Arts and Sciences, Yongchuan, 402160, People’s Republic of China

    Yanhua Cai

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  1. Haili Yu
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  2. Guihua Zhang
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  3. Yanhua Cai
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  4. Faqin Dong
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Correspondence to Faqin Dong.

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Yu, H., Zhang, G., Cai, Y. et al. Altering the substituents of salicylic acid to improve Berthelot reaction for ultrasensitive colorimetric detection of ammonium and atmospheric ammonia. Anal Bioanal Chem 413, 5695–5702 (2021). https://doi.org/10.1007/s00216-021-03485-3

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  • DOI: https://doi.org/10.1007/s00216-021-03485-3

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