Skip to main content
SpringerLink
Log in

Ratiometric fluorescence sensing of formaldehyde in food samples based on bifunctional MOF

  • Original Paper
  • Published:
Microchimica Acta Aims and scope Submit manuscript

Abstract

A new fluorescence strategy was described for ratiometric sensing of formaldehyde (FA) with bifunctional MOF, which acted as a fluorescence reporter as well as biomimetic peroxidase. With the assistance of H2O2, NH2-MIL-101 (Fe) catalyzes the oxidation of non-luminescent substrate o-phenylenediamine (OPD) to produce fluorescent product (oxOPD) with the maximum emission at 570 nm. Besides, intrinsic fluorescence of MOF (λem = 445 nm) was quenched by oxOPD through inner filter effect (IFE). However, FA and OPD reacted to generate Schiff bases, which competitively consumed OPD inhibiting the generation of oxOPD. Under the excitation wavelength of 375 nm, a ratiometric strategy was designed to detect FA with the fluorescence intensity ratio at 445 nm and 570 nm (F445/F570) as readout signal. This strategy exhibited a wide linear range (0.1–50 μM) and low detection limit of 0.03 μM. This method was confirmed for FA detection in food samples. In addition to establishing a new method to detect FA, this work will open new applications of MOF in food safety.

Graphical Abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

Data availability

All data generated or analyzed during this study are included in this article and its supplementary information files.

References

  1. Ding H, Yuan G, Peng L, Zhou L, Lin Q (2020) TP-FRET-based fluorescent sensor for ratiometric detection of formaldehyde in real food samples, living cells, tissues, and zebrafish. J Agric Food Chem 68:3670–3677

    Article  CAS  Google Scholar 

  2. Zhao Q, Shen T, Liu Y, Hu X, Zhao W, Ma Z, Li P, Zhu X, Zhang Y, Liu M, Yao S (2021) Universal nanoplatform for formaldehyde detection based on the oxidase-mimicking activity of MnO2 nanosheets and the in situ catalysis-produced fluorescence species. J Agic Food Chem 69:7303–7312

    Article  CAS  Google Scholar 

  3. Liu C, Shi C, Li H, Du W, Li Z, Wei L, Yu M (2015) Nanomolar fluorescent quantitative detection of formaldehyde with a 8-hydroxyquinoline derivative in aqueous solution and electrospun nanofibers. Sensor Actuat B: Chem 219:185–191

    Article  CAS  Google Scholar 

  4. Yuan G, Ding H, Peng L, Zhou L, Lin Q (2020) A novel fluorescent probe for ratiometric detection of formaldehyde in real food samples, living tissues and zebrafish. Food Chem 331:127221

    Article  CAS  Google Scholar 

  5. Bi A, Gao T, Cao X, Dong J, Liu M, Ding N, Liao W, Zeng W (2018) A novel naphthalimide-based probe for ultrafast, highly selective and sensitive detection of formaldehyde. Sensor Actuat B: Chem 255:3292–3297

    Article  CAS  Google Scholar 

  6. Zhang D, Zhang J, Li M, Aimaiti G, Tuersun G, Ye J, Chu Q (2011) A novel miniaturised electrophoretic method for determining formaldehyde and acetaldehyde in food using 2-thiobarbituric acid derivatization. Food Chem 129:206–212

    Article  CAS  Google Scholar 

  7. Cui X, Fang G, Jiang L, Wang S (2007) Kinetic spectrophometric method for rapid determination of trace formaldehyde in foods. Anal Chim Acta 590:253–259

    Article  CAS  Google Scholar 

  8. Nie X, Chen Z, Tian Y, Chen S, Qu L, Fan M (2021) Rapid detection of trace formaldehyde in food based on surface-enhanced Raman scattering coupled with assembled purge trap. Food Chem 340:127930

    Article  CAS  Google Scholar 

  9. Zhao X, Zhang Z (2009) Microwave-assisted on-line derivatization for sensitive flow injection fluorometric determination of formaldehyde in some foods. Talanta 80:242–245

    Article  CAS  Google Scholar 

  10. Cao Y, Teng Z, Zhang J, Cao T, Qian J, Wang J, Qin W, Guo H (2020) A fluorescent probe for distinguish detection of formaldehyde and acetaldehyde. Sensor Actuat B: Chem 320:128354

    Article  CAS  Google Scholar 

  11. Qu F, Guo Z, Jiang D, Zhao XE (2021) In situ growth of polydopamine on surface of covalent organic frameworks under the catalysis of acid phosphatase for dopamine detection. Chin Chem Lett 32:3368–3371

    Article  CAS  Google Scholar 

  12. He L, Yang X, Ren M, Kong X, Liu Y, Lin W (2016) An ultra-fast illuminating fluorescent probe for monitoring formaldehyde in living cells, shiitake mushrooms, and indoors. Chem Commun 52:9582

    Article  CAS  Google Scholar 

  13. Zhou W, Dong H, Yan H, Shi C, Yu M, Wei L, Li Z (2015) HCHO-reactive molecule with dual-emission-enhancement property for quantitatively detection HCHO in near 100% water solution. Sensor Actuat B: Chem 209:664–669

    Article  CAS  Google Scholar 

  14. Jana A, Baruah M, MunanSamanta S (2021) A ICT based water-soluble fluorescent probe for discriminating mono and dicarbonyl species and analysis in foods. Chem Commun 57:6380

    Article  CAS  Google Scholar 

  15. Zhang Y, Qi J, Li M, Gao D, Xing C (2021) Fluorescence probe based on graphene quantum dots for selective, sensitive and visualized detection formaldehyde in food. Sustainability 13:5273

    Article  CAS  Google Scholar 

  16. Akshath U, Bhatt P (2018) Supramolecular nano-sniffers for ultrasensitive detection of formaldehyde. Biosens Bioelectron 100:201–207

    Article  CAS  Google Scholar 

  17. Akshath U, Bhatt P (2016) Tunneling of redox enzymes to design nano-probes for monitoring NAD+ dependent bio-catalytic activity. Biosens Bioelectron 85:240–246

    Article  CAS  Google Scholar 

  18. Xia M, Zhao XE, Sun J, Zheng ZJ, Zhu SY (2020) Graphene quantum dots combined with the oxidase-mimicking activity of Ce4+ for ratiometric fluorescent detection of Ce4+ and alendronate sodium. Sensor Actuat B: Chem 319:128321

    Article  CAS  Google Scholar 

  19. Liu LY, Zhu SY, Sun J, Xia M, Zhao XE, Xu GB (2021) Ratiometric fluorescence detection of bleomycin based on proximity-dependent fluorescence conversion of DNA-templated silver nanoclusters. Chin Chem Lett 32:906–909

    Article  CAS  Google Scholar 

  20. Shi L, Li N, Wang D, Fan M, Zhang S, Gong Z (2021) Environmental pollution analysis based on the luminescent metal organic frameworks: a review. Trend Anal Chem 134:116131

    Article  CAS  Google Scholar 

  21. Karthik P, Pandikumar A, Preeyanghaa M, Kowsalya M, Neppolian B (2017) Amino-functionalized MIL-101(Fe) metal organic framework as a viable fluorescent probe for nitroaromatic compounds. Microchim Acta 184:2265–2273

    Article  CAS  Google Scholar 

  22. Liu P, Li X, Xu X, Ye K, Wang L, Zhu H, Wang M, Niu X (2021) Integrating peroxidase-mimicking activity with photoluminescence into one framework structure for high-performance ratiometric fluorescent pesticide sensing. Sensor Actuat B: Chem 328:129024

    Article  CAS  Google Scholar 

  23. Li S, Hu X, Chen Q, Zhang X, Chai H, Huang Y (2019) Introducing bifunctional metal-organic frameworks to the construction of a novel ratiometric fluorescence sensor for screening acid phosphatase activity. Biosen Bioelestron 137:133–139

    Article  CAS  Google Scholar 

  24. Xia YH, Sun KM, Zuo YN, Zhu SY, Zhao XE (2022) Fluorescent MOF-based nanozymes for discrimination of phenylenediamine isomers and ratiometric sensing of o-phenylenediamine. Chin Chem Lett 33:2081–2085

    Article  CAS  Google Scholar 

  25. Wang LJ, Wen LJ, Zheng SJ, Tao FF, Chao J, Wang F, Li CL (2022) Integrating peroxidase-mimicking NH2-MIL-101 (Fe) with molecular imprinting for high-performance ratiometric fluorescence sensing of domoic acid. Sensor Actuat B: Chem 361:131688

    Article  CAS  Google Scholar 

  26. Zhao XE, Zuo YN, Xia YH, Sun J, Zhu SY, Xu GB (2022) Multifunctional NH2-Cu-MOF based ratiometric fluorescence assay for discriminating catechol from its isomers. Sensor Actuat B: Chem 371:132548

    Article  CAS  Google Scholar 

  27. Deng L, Liu Q, Lei C, Zhang Y, Huang Y, Nie Z, Yao S (2020) Fluorometric and colorimetric dual-readout assay for histone demethylase activity based on formaldehyde inhibition of Ag+-triggered oxidation of o-phenylenediamine. Anal Chem 92:9421–9428

    Article  CAS  Google Scholar 

  28. Shen J, Wu J, Sun X, Wu Z, Gao P, Liu B (2017) Formaldehyde sensing based on the catalytic reaction of β-HgS nanocrystals. J Mater Chem 5:3757

    CAS  Google Scholar 

  29. Ahamd I, Zhou Z, Li H, Zang S (2020) Crafting CdTe/CdS QDs surface for the selective recognition of formaldehyde gas via ratiometric contrivance. Sensor Actuat B: Chem 304:127379

    Article  Google Scholar 

  30. Liu H, Sun Y, Li Z, Yang J, Aryee A, Qu L, Du D, Lin Y (2019) Lysosome-targeted carbon dots for ratiometric imaging of formaldehyde in living cells. Nanoscale 11:8458

    Article  CAS  Google Scholar 

  31. Li C, Hung J, Zhu H, Liu L, Feng Y, Hu G, Yu X (2017) Dual-emitting fluorescence of Eu/Zr-MOF for ratiometric sensing formaldehyde. Sensor Actuat B: Chem 253:275–282

    Article  CAS  Google Scholar 

  32. Wang XL, Reham A, Kong RM, Cheng YY, Tian XX, Liang MS, Zhang LD, Xia L, Qu FL (2021) Naphthalimide derivative-functionalized metal-organic framework for highly sensitive and selective determination of aldehyde by space confinement-induced sensitivity enhancement effect. Anal Chem 93:8219–8227

    Article  CAS  Google Scholar 

  33. Xu X, Su R, Zhao X, Liu Z, Li D, Li XY, Zhang HQ, Wang ZM (2011) Determination of formaldehyde in beverages using microwave-assisted derivatization and ionic liquid-based dispersive liquid-liquid microextraction followed by high-performance liquid chromatography. Talanta 85:2632–2638

    Article  CAS  Google Scholar 

  34. Li P, Zhang D, Zhang Y, Lu W, Wang W, Chen T (2018) Ultrafast and efficient detection of formaldehyde in aqueous solutions using chitosan-based fluorescent polymers. ACS Sens 3:2394–2401

    Article  CAS  Google Scholar 

  35. Zou G, Guo L, Chen S, Liu N, Yu Y (2022) Multifunctional ratiometric fluorescent sensing platform constructed by grafting various response groups on carbon dots with bromine active site for biosensing and bioimaging. Sensor Actuat B: Chem 357:131376

    Article  CAS  Google Scholar 

  36. Ding H, Yuan G, Peng L, Zhou L, Lin Q (2020) TP-FRET-based fluorescent sensor for ratiometric detection of formaldehyde in real samples, living cells, tissues, and zebrafish. J Agric Food Chem 68:3670–4367

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 22076097, 22176109 and 22174100), the Natural Science Foundation of Shandong Province (No. ZR2020MB066), and the Qinghai Special Project of Innovation Platform for Basic Conditions of Scientific Research of China (No. 2022-ZJ-Y18).

Author information

Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu City, 273165, Shandong, China

    Ya-Nan Zuo, Xian-En Zhao, Yinghui Xia, Zhi-Ang Liu & Shuyun Zhu

  2. Qinghai Key Laboratory of Qinghai-Tibet Plateau Biological Resources, Northwest Institute of Plateau Biology, Chinese Academy of Sciences, Xining City, 810001, Qinghai, China

    Jing Sun

  3. TEM Laboratory, Experimental Teaching and Equipment Management Center, Qufu Normal University, Qufu City, 273165, Shandong, China

    Zhi-Ang Liu

  4. College of Life Sciences, Wuchang University of Technology, Wuhan, 430223, China

    Huwei Liu

Authors
  1. Ya-Nan Zuo
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xian-En Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yinghui Xia
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Zhi-Ang Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jing Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Shuyun Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Huwei Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Xian-En Zhao or Shuyun Zhu.

Ethics declarations

Competing interests

The authors declare no competing interests.

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.

Supplementary file1 (DOCX 1.44 MB)

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.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zuo, YN., Zhao, XE., Xia, Y. et al. Ratiometric fluorescence sensing of formaldehyde in food samples based on bifunctional MOF. Microchim Acta 190, 36 (2023). https://doi.org/10.1007/s00604-022-05607-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00604-022-05607-9

Keywords

Search

Navigation