Colorimetric and fluorometric dual-channel ratiometric determination of fungicide cymoxanil based on analyte-induced aggregation of silver nanoparticles and dually emitting carbon dots

Abstract

A dual-channel ratiometric method is presented for improved colorimetric and fluorometric visualization of the fungicide cymoxanil (CYM). It is based on the use of a mixture of dually emitting carbon dots (CDs) and citrate-stabilized silver nanoparticles (AgNPs). The CDs, under photoexcitation at 350 nm, display dual (blue and green) fluorescence, with peaks at 435 and 520 nm. In mixed aqueous suspension of CDs and AgNPs, the intensity of blue fluorescence of CDs is reduced due to internal filter effect (IFE). This is due to the spectral overlap between the emission of CDs and the absorption of yellow AgNPs. After the addition of CYM to the mixture, CYM triggers the aggregation of AgNPs due to electrostatic attraction and hydrogen bonding interactions. The aggregated AgNPs have an orange color with an absorption whose maximum is shifted to around 510 nm. Hence, it overlaps the green emission of CDs. This causes an IFE on the green fluorescence, while the blue fluorescence is recovered. The colorimetric is performed by ratioing the absorbances at 515 and 390 nm. The ratiometric fluorometric assay is based on ratioing the emissions at 435 and 520 nm. The assay has a wide detection range (0.01–0.55 μΜ) and a low limit of detection (2 nM at S/N = 3). The assay was applied to the determination of CYM in spiked real samples (natural river water, soil and plant epidermis). Recoveries ranged between 97 and 105%. The method enables assays to perform on-site and visual detection by observing fluorescence color shades in either aqueous solutions and on wetted filter paper strips.

Schematic representation of a dual (colorimetric and fluorometric) ratiometric assay for the fungicide cymoxanil (CYM). The method is based on CYM-induced aggregation of silver nanoparticles (AgNPs) and an internal filter effect which induces fluorescence (FL) changes of dually emitting carbon dots (CDs).

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

We’re sorry, something doesn't seem to be working properly.

Please try refreshing the page. If that doesn't work, please contact support so we can address the problem.

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

References

  1. 1.

    Klopping HL, Delp CJ (1980) 2-Cyano-N-[(ethylamino)-carbonyl]-2-(methoxyimino)acetamide, a new fungicide. J Agric Food Chem 28:467–468

    CAS  PubMed  Google Scholar 

  2. 2.

    (1996) Introduction to the genus phytophthora in phytophthora diseases worldwide. Erwin DC, Ribeiro OK (Eds) American phyto- pathological society press, St. Paul

  3. 3.

    (1997) The pesticide manual. Tomlin CDS (ed) British Crop Protection Council, Surrey

  4. 4.

    (1999) Farm chemicals handbook 99. Meister RT (ed) Meister Publishing, Willoughby

  5. 5.

    Brancato A, Brocca D, De Lentdecker C, Erdos Z, Ferreira L, Greco L et al (2017) Modification of the existing maximum residue level for cymoxanil in beans without pods. EFSA J 15:5066

    Google Scholar 

  6. 6.

    Fayette J, Roberts PD, Jones JB, Pernezny KL, Raid RL (2016) Organic compounds increase the efficacy of famoxadone + cymoxanil in the control of bacterial leaf spot of lettuce. Crop Prot 89:47–50

    CAS  Google Scholar 

  7. 7.

    Rodrigues AM, Ferreira V, Cardoso VV, Ferreira E, Benoliel MJ (2007) Determination of several pesticides in water by solid- phase extraction, liquid chromatography and electrospray tandem mass spectrometry. J Chromatogr A 1150:267–278

    CAS  PubMed  Google Scholar 

  8. 8.

    Fibigr J, Šatínský D, Solich P (2018) Current trends in the analysis and quality control of food supplements based on plant extracts. Anal Chim Acta 1036:1–15

    CAS  PubMed  Google Scholar 

  9. 9.

    Liu X, Yang Y, Cui Y, Zhu H, Li X, Li Z et al (2014) Dissipation and residue of metalaxyl and cymoxanil in pepper and soil. Environ Monit Assess 186:5307–5313

    CAS  PubMed  Google Scholar 

  10. 10.

    Huang Z, Zhang Y, Wang L, Ding L, Wang M, Yan H et al (2009) Simultaneous determination of 103 pesticide residues in tea samples by LC-MS/MS. J Sep Sci 32:1294–1301

    CAS  PubMed  Google Scholar 

  11. 11.

    Álvarez-Martín A, Sánchez-Martín MJ, Pose-Juan E, Rodríguez-Cruz MS (2016) Effect of different rates of spent mushroom substrate on the dissipation and bioavailability of cymoxanil and tebuconazole in an agricultural soil. Sci Total Environ 550:495–503

    PubMed  Google Scholar 

  12. 12.

    Álvarez-Martín A, Rodríguez-Cruz MS, Andrades MS, Sánchez-Martín MJ (2016) Application of a biosorbent to soil: a potential method for controlling water pollution by pesticides. Environ Sci Pollut Res 23:9192–9203

    Google Scholar 

  13. 13.

    Balayiannis G, Karasali H, Ambrus A (2014) Rapid determination of famoxadone and cymoxanil in commercial pesticide formulation by high performance liquid chromatography using a C18 monolithic rod column. Bull Environ Contam Toxicol 93:775–780

    CAS  PubMed  Google Scholar 

  14. 14.

    Fidente P, Di Giovanni C, Seccia S, Morrica P (2005) Determination of cymoxanil in drinking water and soil using high- performance liquid chromatography. Biomed Chromatogr 19:766–770

    CAS  PubMed  Google Scholar 

  15. 15.

    Morrica P, Fidente P, Seccia S (2005) High-performance liquid chromatographic mass spectrometric identification of the photo- products of cymoxanil. Biomed Chromatogr 19:506–512

    CAS  PubMed  Google Scholar 

  16. 16.

    de Sabando OL, de Balugera ZG, Goicolea MA, Rodriguez E, Sampedro MC, Barrio RJ (2002) Determination of simazine and cymoxanil in soils by microwave-assisted solvent extraction and HPLC with reductive amperometrical detection. Chromatographia 55:667–671

    Google Scholar 

  17. 17.

    Hengel MJ, Shibamoto T (2001) Development of a gas chromatographic method for fungicide cymoxanil analysis in dried hops. J Agric Food Chem 49:570–573

    CAS  PubMed  Google Scholar 

  18. 18.

    Bavol D, Zima J, Barek J, Dejmkova H (2016) Voltammetric determination of cymoxanil and famoxadone at different types of carbon electrodes. Electroanalysis 28:1029–1034

    CAS  Google Scholar 

  19. 19.

    Mercan H, Inam R (2010) Determination of cymoxanil fungicide in commercial formulation and natural water by square-wave stripping voltammetry. Clean: Soil Air Water 38:558–564

    CAS  Google Scholar 

  20. 20.

    Xia X, He Q, Dong Y, Deng R, Li J (2018) Aptamer-based homogeneous analysis for food control. Curr Anal Chem. https://doi.org/10.2174/1573411014666180810125737

  21. 21.

    Chen Z, Liu Y, Wang Y, Zhao X, Li J (2013) Dynamic monitoring of cell surface n-glycan expression via electrogenerated chemiluminescence cytosensor integrating concanavalin a and gold nanoparticles modified (Rubpy)3 2+-doped silica nanoprobe. Anal Chem 85:4431–4438

    CAS  PubMed  Google Scholar 

  22. 22.

    Tang L, Li J (2017) Plasmon–enhanced colorimetric nanosensors for ultrasensitive molecular diagnostics. ACS Sens 2:857–875

    CAS  PubMed  Google Scholar 

  23. 23.

    Wang Y, Tang L, Li Z, Lin Y, Li J (2014) In situ simultaneous monitoring of ATP and GTP using graphene oxide nanosheets- based sensing platform in living cells. Nat Protoc 9:1944–1955

    CAS  PubMed  Google Scholar 

  24. 24.

    Fan JL, Hu MM, Zhan P, Peng XJ (2013) Energy transfer cassettes based on organic fluorophores: construction and applications in ratiometric sensing. Chem Soc Rev 42:29–43

    CAS  PubMed  Google Scholar 

  25. 25.

    Lee MH, Kim JS, Sessler JL (2015) Small molecule-based ratiometric fluorescence probes for cations, anions, and biomolecules. Chem Soc Rev 44:4185–4191

    CAS  PubMed  Google Scholar 

  26. 26.

    Wu P, Hou XD, Xu JJ, Chen HY (2016) Ratiometric fluorescence, electrochemiluminescence, and photoelectrochemical chemo/ biosensing based on semiconductor quantum dots. Nanoscale 8:8427–8442

    CAS  PubMed  Google Scholar 

  27. 27.

    Huang XL, Song JB, Yung BC, Huang XH, Xiong YH, Chen XY (2018) Ratiometric optical nanoprobes enable accurate molecular detection and imaging. Chem Soc Rev 47:2873–2920

    CAS  PubMed  PubMed Central  Google Scholar 

  28. 28.

    Fu Y, Jin H, Bu X, Gui R (2018) Melamine-induced decomposition and anti-FRET effect from self-assembled complex of rhodamine 6G and DNA-stabilized silver nanoclusters used for dual-emitting ratiometric and naked-eye visual fluorescence detection. J Agric Food Chem 66:9819–9827

    CAS  PubMed  Google Scholar 

  29. 29.

    He W, Gui R, Jin H, Wang B, Bu X, Fu Y (2018) Ratiometric fluorescence and visual imaging detection of dopamine based on carbon dots/copper nanoclusters dual-emitting nanohybrids. Talanta 178:109–115

    CAS  PubMed  Google Scholar 

  30. 30.

    Gui R, Bu X, He W, Jin H (2018) Ratiometric fluorescence solution-phase and filter-paper visualization detection of ciprofloxacin based on dual-emitting carbon dots/silicon dots hybrids. New J Chem 42:16217–16225

    CAS  Google Scholar 

  31. 31.

    Bu X, Fu Y, Jin H, Gui R (2018) Specific enzymatic synthesis of 2,3-diaminophenazine and copper nanoclusters used for dual- emission ratiometric and naked-eye visual fluorescence sensing of choline. New J Chem 42:17323–17330

    CAS  Google Scholar 

  32. 32.

    Jin H, Gui R, Yu J, Lv W, Wang Z (2017) Fabrication strategies, sensing modes and analytical applications of ratiometric electrochemical biosensors. Biosens Bioelectron 91:523–537

    CAS  PubMed  Google Scholar 

  33. 33.

    Jin H, Zhao C, Gui R, Gao X, Wang Z (2018) Reduced graphene oxide/nile blue/gold nanoparticles complex-modified glassy carbon electrode used as a sensitive and label-free aptasensor for ratiometric electrochemical sensing of dopamine. Anal Chim Acta 1025:154–162

    CAS  PubMed  Google Scholar 

  34. 34.

    Gui R, Wan A, Zhang Y, Li H, Zhao T (2014) Ratiometric and time-resolved fluorimetry from quantum dots featuring drug carriers for real-time monitoring of drug release in situ. Anal Chem 86:5211–5214

    CAS  PubMed  Google Scholar 

  35. 35.

    Gui R, Jin H, Bu X, Fu Y, Wang Z, Liu Q (2019) Recent advances in dual-emission ratiometric fluorescence probes for chemo/ biosensing and bioimaging of biomarkers. Coord Chem Rev 383:82–103

    CAS  Google Scholar 

  36. 36.

    Zu F, Yan F, Bai Z, Xu J, Wang Y, Huang Y, Zhou X (2017) The quenching of the fluorescence of carbon dots: a review on mechanisms and applications. Microchim Acta 184:1899–1914

    CAS  Google Scholar 

  37. 37.

    Ivrigh ZJN, Fahimi-Kashani N, Hormozi-Nezhad MR (2017) Aggregation-based colorimetric sensor for determination of prothioconazole fungicide using colloidal silver nanoparticles (AgNPs). Spectrochim Acta A 187:143–148

    CAS  Google Scholar 

  38. 38.

    Ma Y, Chen Y, Liu J, Han Y, Ma S, Chen X (2018) Ratiometric fluorescent detection of chromiumVI. In real samples based on dual emissive carbon dots. Talanta 185:249–257

    CAS  PubMed  Google Scholar 

  39. 39.

    Nijegorodov N, Mabbs R, Winkoun DP (2003) Influence of weak and strong donor groups on the fluorescence parameters and the intersystem crossing rate constant. Spectrochim Acta A 59:595–606

    CAS  Google Scholar 

  40. 40.

    Song Y, Zhu S, Zhang S, Fu Y, Wang L, Zhao X et al (2015) Investigation from chemical structure to photoluminescent mechanism: a type of carbon dots from the pyrolysis of citric acid and an amine. J Mater Chem C 3:5976–5984

    CAS  Google Scholar 

  41. 41.

    Zheng Y, Yang D, Wu X, Yan H, Zhao Y, Feng B et al (2015) A facile approach for the synthesis of highly luminescent carbon dots using vitaminbased small organic molecules with benzene ring structure as precursors. RSC Adv 5:90245–90254

    CAS  Google Scholar 

  42. 42.

    Yu P, Wen X, Toh YR, Tang J (2012) Temperature-dependent fluorescence in carbon dots. J Phys Chem C 116:25552–25557

    CAS  Google Scholar 

  43. 43.

    Wen X, Yu P, Toh YR, Hao X, Tang J (2013) Intrinsic and extrinsic fluorescence in carbon nanodots: ultrafast time-resolved fluorescence and carrier dynamics. Adv Opt Mater 1:173–178

    Google Scholar 

  44. 44.

    Zhu S, Song Y, Zhao X, Shao J, Zhang J, Yang B (2015) The photoluminescence mechanism in carbon dots (graphene quantum dots, carbon nanodots, and polymer dots): current state and future perspective. Nano Res 8:355–381

    CAS  Google Scholar 

  45. 45.

    Agnihotri S, Mukherji S, Mukherji S (2014) Size-controlled silver nanoparticles synthesized over the range 5–100 nm using the same protocol and their antibacterial efficacy. RSC Adv 4:3974–3983

    CAS  Google Scholar 

  46. 46.

    Miao P, Liu T, Li X, Ning L, Yin J, Han K (2013) Highly sensitive, label-free colorimetric assay of trypsin using silver nanoparticles. Biosens Bioelectron 49:20–24

    CAS  PubMed  Google Scholar 

  47. 47.

    Augusto J, Brenneman T (2012) Assessing systemicity of peanut fungicides through bioassay of plant tissues with Sclerotium rolfsii. Plant Dis 96:330–337

    CAS  PubMed  Google Scholar 

  48. 48.

    Sanematsu K, Kitagawa M, Yoshida R, Nirasawa S, Shigemura N, Ninomiya Y (2016) Intracellular acidification is required for full activation of the sweet taste receptor by miraculin. Sci Rep 6:22807

    CAS  PubMed  PubMed Central  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the Natural Science Foundation of Shandong (ZR2019MB026) and the Source Innovation Plan Application Basic Research Project of Qingdao (17-1-1-72-jch and 18-2-2-26-jch).

Author information

Affiliations

Authors

Corresponding author

Correspondence to Rijun Gui.

Ethics declarations

The author(s) declare that they have no competing interests.

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

(DOC 503 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Jiang, X., Jin, H., Sun, Y. et al. Colorimetric and fluorometric dual-channel ratiometric determination of fungicide cymoxanil based on analyte-induced aggregation of silver nanoparticles and dually emitting carbon dots. Microchim Acta 186, 580 (2019). https://doi.org/10.1007/s00604-019-3697-x

Download citation

Keywords

  • Silver nanoparticles
  • Carbon dots
  • Ratiometric fluorescence
  • Cymoxanil
  • Visual detection