Abstract
Development of effective methods for analyzing hypochlorite is of great significance due to the crucial role of hypochlorite in live organisms, as an endogenously produced reactive oxygen species (ROS) in the human immune system. In this paper, a novel fluorescent probe based on 6-methylthiocoumarinyl formate was designed and synthesized in one step for detection of hypochlorite in MeCN/PBS (8:2, v/v, pH 7.4) medium. The probe showed high specificity for hypochlorite over other competitive ROS analytes, extreme large Stokes shift of 265 nm, rapid response to hypochlorite within 20 s, low detection limit of 1.57 μM, and a wide applicable range of pH 3–10. The sensing mechanism was demonstrated to be based on oxidation of methyl phenyl sulfide to sulfoxide by hypochlorite. The probe may have extensive application for selective and convenient detection of hypochlorite due to its multiple advantages.
Similar content being viewed by others
Data availability
The authors confirm that the data supporting the findings of this study are available within the article.
References
Baruah M, Kwon H-Y, Cho H, Chang Y-T, Samanta A (2023) A photoinduced electron transfer-based hypochlorite-specific fluorescent probe for selective imaging of proinflammatory M1 in a rheumatoid arthritis model. Anal Chem 95:4147–4154. https://doi.org/10.1021/acs.analchem.2c05218
Casciaro M, Di Salvo E, Pace E, Ventura-Spagnolo E, Navarra M, Gangemi S (2017) Chlorinative stress in age-related diseases: a literature review. Immun Ageing 14:21. https://doi.org/10.1186/s12979-017-0104-5
Chang C, Wang F, Qiang J, Zhang Z, Chen Y, Zhang W, Wang Y, Chen X (2017) Benzothiazole-based fluorescent sensor for hypochlorite detection and its application for biological imaging. Sens Actuators B 243:22–28. https://doi.org/10.1016/j.snb.2016.11.123
Chen X, Tian X, Shin I, Yoon J (2011) Fluorescent and luminescent probes for detection of reactive oxygen and nitrogen species. Chem Soc Rev 40:4783–4804. https://doi.org/10.1039/c1cs15037e
Chen X, Wang F, Hyun JY, Wei T, Qiang J, Ren X, Shin I, Yoon J (2016) Recent progress in the development of fluorescent, luminescent and colorimetric probes for detection of reactive oxygen and nitrogen species. Chem Soc Rev 45:2976–3016. https://doi.org/10.1039/c6cs00192k
Chen W, Li G, Chen C, Sheng J, Yang L (2020) Aggregation-enhanced emission enables phenothiazine coumarin as a robust ratiometric fluorescent for rapid and selective detection of HClO. Spectrochim Acta A 228:117724. https://doi.org/10.1016/j.saa.2019.117724
Cheng G, Fan J, Sun W, Cao J, Hu C, Peng X (2014) A near-infrared fluorescent probe for selective detection of HClO based on se-sensitized aggregation of heptamethine cyanine dye. Chem Commun 50:1018–1020. https://doi.org/10.1039/c3cc47864e
Cheshchevik VT, Krylova NG, Cheshchevik NG, Lapshina EA, Semenkova GN, Zavodnik IB (2021) Role of mitochondrial calcium in hypochlorite induced oxidative damage of cells. Biochimie 184:104–115. https://doi.org/10.1016/j.biochi.2021.02.009
Debnath S, Ghosh R, Nair RR, Pradhan D, Chatterjee PB (2022) Advances in the development of water-soluble fluorogenic probes for bioimaging of hypochlorite/hypochlorous acid in cells and organisms. ACS Omega 7:38122–38149. https://doi.org/10.1021/acsomega.2c04840
Dong S, Zhang L, Lin Y, Ding C, Lu C (2020) Luminescent probes for hypochlorous acid in vitro and in vivo. Analyst 145:5068–5089. https://doi.org/10.1039/d0an00645a
Duan C, Won M, Verwilst P, Xu J, Kim HS, Zeng L, Kim JS (2019) In vivo imaging of endogenously produced HClO in zebrafish and mice using a bright, photostable ratiometric fluorescent probe. Anal Chem 91:4172–4178. https://doi.org/10.1021/acs.analchem.9b00224
Gomes A, Fernandes E, Lima JLFC (2005) Fluorescence probes used for detection of reactive oxygen species. J Biochem Biophys Methods 65:45–80. https://doi.org/10.1016/j.jbbm.2005.10.003
He S, Fang W-L, Guo X-F, Wang H, Samanta A (2023) A water-soluble two-photon fluorescent probe for rapid and reversible monitoring of redox state. Talanta 253:124066. https://doi.org/10.1016/j.talanta.2022.124066
Hou J-T, Wang B, Fan P, Duan R, Cao X, Zhu L, Wang S (2020) A novel benzothiazine-fused coumarin derivative for sensing hypochlorite with high performance. Dyes Pigm 182:108675. https://doi.org/10.1016/j.dyepig.2020.108675
Hou J-T, Wang B, Zou Y, Fan P, Chang X, Cao X, Wang S, Yu F (2020) Molecular fluorescent probes for imaging and evaluation of hypochlorite fluctuations during diagnosis and therapy of osteoarthritis in cells and in a mouse model. ACS Sens 5:1949–1958. https://doi.org/10.1021/acssensors.0c00270
Jackson DS, Crockett DF, Wolnik KA (2006) The indirect detection of bleach (sodium hypochlorite) in beverages as evidence of product tampering. J Forens Sci 51:827–831. https://doi.org/10.1111/j.1556-4029.2006.00160.x
Jin Y, Lv M, Tao Y, Xu S, He J, Zhang J, Zhao W (2019) A water-soluble BODIPY-based fluorescent probe for rapid and selective detection of hypochlorous acid in living cells. Spectrochim Acta A 219:569–575. https://doi.org/10.1016/j.saa.2019.04.085
Kailasa SK, Vajubhai GN, Koduru JR, Park TJ (2023) Recent progree of nanomaterials for colorimetric and fluorescence sensing of reactive oxygen species in biological and environmental samples. Trends Environ Anal Chem 37:e00196. https://doi.org/10.1016/j.teac.2023.e00196
Kateshiya MR, Malek NI, Kailasa SK (2022) Green fluorescent carbon dots functionalized MoO3 nanoparticles for sensing of hypochlorite. J Mol Liq 351:118628. https://doi.org/10.1016/j.molliq.2022.118628
Kim T-I, Park S, Choi Y, Kim Y (2011) A BODIPY-based probe for the selective detection of hypochlorous acid in living cells. Chem Asian J 6:1358–1361. https://doi.org/10.1002/asia.201100025
Kim Y, Choi M, Manjare ST, Jon S, Churchill DG (2016) Diselenide-based probe for the selective imaging of hypochlorite in living cancer cells. RSC Adv 6:32013–32017. https://doi.org/10.1039/c6ra04257k
Li P, Jia Y, Zhao N, Zhang Y, Zhou P, Lou Z, Qiao Y, Zhang P, Wen S, Han K (2020) Quantifying the fast dynamics of HClO in living cells by a fluorescent probe capable of responding to oxidation and reduction events within the time scale of milliseconds. Anal Chem 92:12987–12995. https://doi.org/10.1021/acs.analchem.0c01703
Li S, Wang P, Liu Y, Yang K, Zhong R, Cheng D, He L (2023) A mitochondrial-targeted near-infrared fluorescent probe for visualizing the fluctuation of hypochlorite acid in idiopathic pulmonary fibrosis mice. Anal Chim Acta 1239:340731. https://doi.org/10.1016/j.aca.2022.340731
Liu S-R, Wu S-P (2013) Hypochlorous acid turn-on fluorescent probe based on oxidation of diphenyl selenide. Org Lett 15:878–881. https://doi.org/10.1021/ol400011u
Liu S-R, Vedamalai M, Wu S-P (2013) Hypochlorous acid turn-on boron dipyrromethene probe based on oxidation of methyl phenyl sulfide. Anal Chim Acta 800:71–76. https://doi.org/10.1016/j.aca.2013.09.018
Liu F, Gao Y, Wang J, Sun S (2014) Reversible and selective luminescent determination of ClO–/H2S redox cycle in vitro and in vivo based on a ruthenium trisbipyridyl probe. Analyst 139:3324–3329. https://doi.org/10.1039/c4an00331d
Liu C, Wang Q, Jiao X, Yao H, He S, Zhao L, Zeng X (2019) A ratiometric fluorescent probe for hypochlorous acid and its biological applications. Dyes Pigm 160:989–994. https://doi.org/10.1016/j.dyepig.2018.07.001
Lou Z, Li P, Pan Q, Han K (2013) A reversible fluorescent probe for detecting hypochloric acid in living cells and animals: utilizing a novel strategy for effectively modulating the fluorescence of selenide and selenoxide. Chem Commun 49:2445–2447. https://doi.org/10.1039/c3cc39269d
Manjare ST, Kim J, Lee Y, Churchill DG (2014) Facile meso-BODIPY annulation and selective sensing of hypochlorite in water. Org Lett 16:520–523. https://doi.org/10.1021/ol403405n
Mulay SV, Choi M, Jang YJ, Kim Y, Jon S, Churchill DG (2016) Enhanced fluorescence turn-on imaging of hypochlorous acid in living immune and cancer cells. Chem Eur J 22:9642–9648. https://doi.org/10.1002/chem.201601270
Ordeig O, Mas R, Gonzalo J, Del Campo J, Muñoz FJ, de Haro C (2005) Continuous detection of hypochlorous acid/hypochlorite for water quality monitoring and control. Electroanalysis 17:1641–1648. https://doi.org/10.1002/elan.200403194
Piel I, Steinmetz M, Hirano K, Froehlich R, Grimme S, Glorius F (2011) Highly asymmetric NHC-catalyzed hydroacylation of unactivated alkenes. Angew Chem Int Ed 50:4983–4987. https://doi.org/10.1002/anie.201008081
Prokopowicz Z, Arce F, Biedroń R, Chiang CL-L, Ciszek M, Katz DR, Nowakowska M, Zapotoczny S, Marcinkiewicz J, Chain BM (2010) Hypochlorous acid: a natural adjuvant that facilitates antigen processing, cross-priming, and the induction of adaptive immunity. J Immunol 184:824–835. https://doi.org/10.4049/jimmunol.0902606
Qu Z, Ding J, Zhao M, Li P (2015) Development of a selenide-based fluorescent probe for imaging hypochlorous acid in lysosomes. J Photochem Photobiol A 299:1–8. https://doi.org/10.1016/j.photochem.2014.10.015
Singh AP, Tsay OG, Murale DP, Jun T, Liew H, Suh Y-H, Churchill DG (2013) Extremely selective “turn-on” fluorescence detection of hypochlorite confirmed by proof-of-principle neurological studies via esterase action in living cells. Analyst 138:2829–2832. https://doi.org/10.1039/c3an00297g
Song X, Shen H, Yin X, Wang X, Lin J (2013) Microflow-injection chemiluminescence of luminol and hypochlorite enhanced by phloxine B. Luminescence 28:16–22. https://doi.org/10.1002/bio.1388
Soni D, Gangada S, Duvva N, Roy TK, Nimesh S, Arya G, Giribabu L, Chitta R (2017) Hypochlorite-promoted inhibition of photo-induced electron transfer in phenothiazine-borondipyrromethene donor-acceptor dyad: a cost-effective and metal-free “turn-on” fluorescent chemosensor for hypochlorite. New J Chem 41:5322–5333. https://doi.org/10.1039/c7nj00516d
Vedamalai M, Kedaria D, Vasita R, Gupta I (2018) Oxidation of phenothiazine based fluorescent probes for hypochlorite and its application to live cell imaging. Sens Actuators B 263:137–142. https://doi.org/10.1016/j.snb.2018.02.071
Venkatesan P, Wu S-P (2015) A turn-on fluorescent probe for hypochlorous acid based on the oxidation of diphenyl telluride. Analyst 140:1349–1355. https://doi.org/10.1039/c4an02116a
Wang B, Li P, Yu F, Song P, Sun X, Yang S, Lou Z, Han K (2013) A reversible fluorescence probe based on se-BODIPY for the redox cycle between HClO oxidative stress and H2S repair in living cells. Chem Commun 49:1014–1016. https://doi.org/10.1039/c2cc37803e
Wang X, Zhou L, Qiang F, Wang F, Wang R, Zhao C (2016) Development of a BODIPY-based ratiometric fluorescent probe for hypochlorous acid and its application in living cells. Anal Chim Acta 911:114–120. https://doi.org/10.1016/j.aca.2016.01.022
Wang S, Zhu B, Wang B, Cao X, Zhu L, Hou J-T, Zeng L (2021) Revealing HOCl burst from endoplasmic reticulum in cisplatin-treated cells via a ratiometric fluorescent probe. Chinese Chem Lett 32:1795–1798. https://doi.org/10.1016/j.cclet.2020.12.039
Wang H, Zhang C, Jiang Z, Xu L, Liu Z (2023) Fluorescent phenothiazine-fused boron complexes for ratiometric hypochlorite imaging. Dalton Trans 52:1393–1398. https://doi.org/10.1039/d2dt03824b
Wu D, Chen L, Xu Q, Chen X, Yoon J (2019) Design principles, sensing mechanisms, and applications of highly specific fluorescent probes for HOCl/OCl–. Acc Chem Res 52:2158–2168. https://doi.org/10.1021/acs.accounts.9b00307
Xiao H, Xin K, Dou H, Yin G, Quan Y, Wang R (2015) A fast-responsive mitochondria-targeted fluorescent probe detecting endogenous hypochlorite in living RAW 264.7 cells and nude mouse. Chem Commun 51:1442–1445. https://doi.org/10.1039/c4cc07411d
Yudhistira T, Mulay SV, Kim Y, Halle MB, Churchill DG (2019) Imaging of hypochlorous acid by fluorescence and applications in biological systems. Chem Asian J 14:3048–3084. https://doi.org/10.1002/asia.201900672
Yue Y, Huo F, Yin C, Escobedo JO, Strongin RM (2016) Recent progress in chromogenic and fluorogenic chemosensors for hypochlorous acid. Analyst 141:1859–1873. https://doi.org/10.1039/c6an00158k
Zhang J, Wang X, Yang X (2012) Colorimetric determination of hypochlorite with unmodified gold nanoparticles through the oxidation of a stabilizer thiol compound. Analyst 137:2806–2812. https://doi.org/10.1039/c2an35239g
Zhang Y-R, Liu Y, Feng X, Zhao B-X (2017) Recent progress in the development of fluorescent probes for the detection of hypochlorous acid. Sens Actuators B 240:18–36. https://doi.org/10.1016/j.snb.2016.08.066
Zhang R, Song B, Yuan J (2018) Bioanalytical methods for hypochlorous acid detection: recent advances and challenges. Trend Anal Chem 99:1–33. https://doi.org/10.1016/j.trac.2017.11.015
Acknowledgements
The funding for the Open Research Program of State Key Laboratory of Molecular Engineering of Polymers, Fudan University (K2022-38 to Yanxi Song) is acknowledged.
Funding
This work was supported by the Funding for the Open Research Program of State Key Laboratory of Molecular Engineering of Polymers, Fudan University (K2022-38 to Yanxi Song).
Author information
Authors and Affiliations
Contributions
Yu Shi developed the idea of the study and was responsible for data collection and draft writing. Baijun Zhao completed measurement of the sensing performance of the probe. Ji Fan and Yong Zhao synthesized the probe and were responsible for data collection and analysis. Yanxi Song was responsible for experiments guiding, sourcing, and paper reviewing. Ziyun Lin participated in probe synthesis and structural characterization. Zhiyu Shao was responsible for paper reviewing and guiding. Hongqi Li was responsible for experiments guiding and paper reviewing.
Corresponding author
Ethics declarations
Conflict of interest
We declare that we do not have any commercial or associative interest that represents a conflict of interest in connection with the work submitted.
Consent for publication
Consent for publication was obtained from all participants.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Shi, Y., Zhao, B., Fan, J. et al. Facile access to a methylthiocoumarinyl formate as highly selective and sensitive fluorescent probe for hypochlorite. Chem. Pap. 78, 3607–3615 (2024). https://doi.org/10.1007/s11696-024-03331-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11696-024-03331-7