Abstract
Nitric oxide (NO) plays an important role in the generation of smog and ozone. Although great efforts have been made to determine NO by using o-phenylenediamine (OPD)-based fluorescent probes, more simple and reliable colorimetric assays for detection of NO are extremely scarce because a single OPD structure cannot produce enough optical absorption for chromogenesis. In this study, we report an innovative two-in-one visual colorimetric methodology. Commercially available 3,3′-diaminobenzidine (DAB) with two OPD structures in a single molecule is selected as the colorimetric probe, and it reacts with NO via diazo-coupling reaction to generate 1H,3’H-[5,5′]bibenzotriazolyl because of the increase of conjugated double bonds, accompanying a distinct color change from colorless to brownish yellow. This two-in-one colorimetric assay can determine NO at a concentration as low as 3 ppm by the naked eye and 40 ppb by UV-vis spectrometry, which is the lowest limit of detection (LOD) among reported colorimetric assays for NO. Moreover, the present two-in-one visual colorimetric assay also has good selectivity toward NO over other common potential gas interferents such as CO2, NO2, NH3, N2, O2, and SO2. This present study provides a new insight for the design and development of assays for NO.

Graphical abstract
This is a preview of subscription content, access via your institution.




References
Weiss R, Craig H. Production of atmospheric nitrous oxide by combustion. Geophys Res Lett. 1976;3:751–3.
Wuebbles DJ. Nitrous oxide: no laughing matter. Science. 2009;326:56–7.
Li K, Jacob DJ, Liao H, Shen L, Zhang Q, Bates KH. Anthropogenic drivers of 2013-2017 trends in summer surface ozone in China. Proc Natl Acad Sci. 2019;116:422–7.
Wang HL, Liu FT, Ding AX, Ma SF, He L, Lin L, et al. Water-soluble Hantzsch ester as switch-on fluorescent probe for efficiently detecting nitric oxide. Spectrochim Acta A. 2016;169:1–6.
Huang CB, Huang J, Xu L. A highly selective fluorescent probe for fast detection of nitric oxide in aqueous solution. RSC Adv. 2015;5:13307–10.
Kleinman LI. Low and high NOx tropospheric photochemistry. J Geophys Res Atmos. 1994;99:16831–8.
Nagano T. Practical methods for detection of nitric oxide. Luminescence. 1999;14:283–90.
Mordvintcev P, Mülsch A, Busse R, Vanin A. On-line detection of nnitric oxide formation in liquid aqueous phase by electron paramagnetic resonance spectroscopy. Anal Biochem. 1991;199:142–6.
Planchet E, Kaiser WM. Nitric oxide (NO) detection by DAF fluorescence and chemiluminescence: a comparison using abiotic and biotic NO sources. J Exp Bot. 2006;57:3043–55.
Wany A, Gupta AK, Kumari A, Gupta S, Mishra S, Jaintu R, et al. Chemiluminescence detection of nitric oxide from roots, leaves, and root mitochondria. Methods Mol Biol. 2016;1424:15–29.
Tsikas D. Simultaneous derivatization and quantification of the titric oxide metabolites nitrite and nitrate in biological fluids by gas chromatography/mass spectrometry. Anal Chem. 2000;72:4064–72.
Privett BJ, Shin JH, Schoenfisch M. Electrochemical nitric oxide sensors for physiological measurements. Chem Soc Rev. 2010;39:1925–35.
Soleymani J, Hasanzadeh M, Somi MH, Jouyban A. Nanomaterials based optical biosensing of hepatitis: recent analytical advancements. TrAC Trends Anal Chem. 2018;107:169–80.
Ding Y, Wang S, Li J, Chen L. Nanomaterial-based optical sensors for mercury ions. TrAC Trends Anal Chem. 2016;82:175–90.
Liu Y, Deng Y, Dong H, Liu K, He N. Progress on sensors based on nanomaterials for rapid detection of heavy metal ions. Sci China Chem. 2017;60:329–37.
Ai R, He Y. Covalent organic framework-inspired chromogenic system for visual colorimetric detection of carcinogenic 3, 3′-diaminobenzidine. Sensors Actuators B Chem. 2020;304:127372.
Zhao M, Wang J, Yu H, He Y, Duan T. A highly selective and sensitive colorimetric assay for specific recognition element-free detection of uranyl ion. Sensors Actuators B Chem. 2020;307:127664.
Du J, Wang J, Deng Y, He Y. Plasmonic hot electron transfer-induced multicolor MoO3-x-based chromogenic system for visual and colorimetric determination of silver(I). Microchim Acta. 2020;187:120.
Huang W, Wang J, Du J, Deng Y, He Y. Contrary logic pairs and circuits using a visually and colorimetrically detectable redox system consisting of MoO3-x nanodots and 3,3′-diaminobenzidine. Microchim Acta. 2019;186:79.
Ray PC, Khan SA, Singh AK, Senapati D, Fan Z. Nanomaterials for targeted detection and photothermal killing of bacteria. Chem Soc Rev. 2012;41:3193–209.
Yaling Y, Yi H. A sensitive and selective method for visual chronometric detection of copper (II) ions using clock reaction. Anal Sci. 2018:18P345.
Mao Z, Feng W, Li Z, Zeng L, Lv W, Liu Z. NIR in, far-red out: developing a two-photon fluorescent probe for tracking nitric oxide in deep tissue. Chem Sci. 2016;7:5230–5.
Wu W, Guan R, Liao X, Yan X, Rees TW, Ji L, et al. Bimodal visualization of endogenous nitric oxide in lysosomes with a two-photon iridium (III) phosphorescent probe. Anal Chem. 2019;91:10266–72.
Wu J, Jiang L, Verwilst P, An J, Zeng H, Zeng L, et al. A colorimetric and fluorescent lighting-up sensor based on ICT coupled with PET for rapid, specific and sensitive detection of nitrite in food. Chem Commun. 2019;55:9947–50.
Kojima H, Nakatsubo N, Kikuchi K, Kawahara S, Kirino Y, Nagoshi H, et al. Detection and imaging of nitric oxide with novel fluorescent indicators: diaminofluoresceins. Anal Chem. 1998;70:2446–53.
Li H, Wan A. Fluorescent probes for real-time measurement of nitric oxide in living cells. Analyst. 2015;140:7129–41.
Liu X, Liu S, Liang G. Fluorescence turn-on for the highly selective detection of nitric oxide in vitro and in living cells. Analyst. 2016;141:2600–5.
Plater MJ, Greig I, Helfrich MH, Ralston SH. The synthesis and evaluation of o-phenylenediamine derivatives as fluorescent probes for nitric oxide detection. J Chem Soc Perkin Trans. 2001;20:2553–9.
Maloney C, Byrne H, Dennis W, Blau W, Kelly J. Picosecond optical phase conjugation using conjugated organic molecules. Chem Phys. 1988;121:21–39.
Zhang J, Cui Y, Wang M, Liu J. Synthesis of double-conjugated-segment molecules and their application as ultra-broad two-photon-absorption optical limiters. Chem Commun. 2002;21:2526–7.
Batchelder D. Colour and chromism of conjugated polymers. Contemp Phys. 1988;29:3–31.
O'Shaughnessy M, Rodebush W. Ultraviolet absorption spectra of organic molecules: the dependence upon restricted rotation and resonance. J Am Chem Soc. 1940;62:2906–11.
Gierschner J, Cornil J, Egelhaaf HJ. Optical bandgaps of π-conjugated organic materials at the polymer limit: experiment and theory. Adv Mater. 2007;19:173–91.
Sun Y, Chen S, Chen X, Xu Y, Zhang S, Ouyang Q, et al. A highly selective and recyclable NO-responsive nanochannel based on a spiroring opening-closing reaction strategy. Nat Commun. 2019;10:1323–30.
Zimmermann F, Lippert T, Beyer C, Stebani J, Nuyken O, Wokaun A. N= N vibrational frequencies and fragmentation patterns of substituted 1-aryl-3, 3-dialkyl-triazenes: comparison with other high-nitrogen compounds. Appl Spectrosc. 1993;47:986–93.
Grimmel H, Morgan JF. Reaction of diazo compounds with sulfamic acid. J Am Chem Soc. 1948;70:1750–1.
Martí A, Costero AM, Gaviña P, Parra M. Selective colorimetric NO (g) detection based on the use of modified gold nanoparticles using click chemistry. Chem Commun. 2015;51:3077–9.
Rodríguez-Nuévalos S, Parra M, Ceballos S, Gil S, Costero AM. A nitric oxide induced “click” reaction to trigger the aggregation induced emission (AIE) phenomena of a tetraphenyl ethylene derivative: a new fluorescent probe for NO. J Photochem Photobiol A. 2020;338:112132.
Acknowledgements
We gratefully acknowledge the financial support of the National Natural Science Foundation of China (41831285) and Longshan Scholars Programme of Southwest University of Science and Technology (Grant No. 18LZX528).
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare they have no conflict of interest.
Research involving human participants and/or animals
The authors declare that no human participants and/or animals were involved in this research.
Additional information
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
ESM 1
(PDF 295 kb)
Rights and permissions
About this article
Cite this article
Yu, H., Dong, F., Chen, J. et al. 3, 3′-Diaminobenzidine with dual o-phenylenediamine groups: two in one enables visual colorimetric detection of nitric oxide. Anal Bioanal Chem 412, 2545–2550 (2020). https://doi.org/10.1007/s00216-020-02482-2
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00216-020-02482-2
Keywords
- 3,3′-Diaminobenzidine
- Two-in-one detection
- Colorimetry
- Nitric oxide
- Visulation