Skip to main content
SpringerLink
Log in

N, P-co-doped carbon dots as a dual-mode colorimetric/ratiometric fluorescent sensor for formaldehyde and cell imaging via an aminal reaction-induced aggregation process

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

Abstract

Novel colorimetric and ratiometric fluorometric dual-mode N, P-co-doped carbon nanodots, BPEI-CDs, for highly sensitive and selective detection of formaldehyde (FA) were successfully prepared from N-(phosphonomethyl)iminodiacetic acid (PMIDA) and branched polyethyleneimine (BPEI). The treatment of FA caused a remarkable linear enhancement of ratiometric fluorescence (F501 nm/F408 nm) in a wide range of 0–40 μM with a detection limit (LOD) of 0.47 μM (3σ/k), along with distinct color changes from colorless to light yellow. Mechanistic study shows that this electron-rich system, formed by the cooperative roles of N and P, promoted the FA-induced Schiff bases formation reaction, which contributed to the CD aggregation-induced emission (AIE) “turn-on” response and enhancement of π-conjugation-induced bathochromic behaviors. Furthermore, N, P-co-doped BPEI-CDs were successfully applied to the determination of FA in bean sprout samples. Using the standard addition method, the recoveries ranged from 96.9 to 101.8%, and the relative standard deviation (RSD) was in the range 2.23 to 3.21%. The application for intracellular FA sensing further verified that this novel nanoprobe may offer a new venue for the design of simple, low-cost, and sensitive biosensors.

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

References

  1. Bruemmer KJ, Green O, Su TA, Shabat D, Chang CJ (2018) Chemiluminescent probes for activity-based sensing of formaldehyde released from folate degradation in living mice. Angew Chem Int Ed 57:7508–7512

    Article  CAS  Google Scholar 

  2. Ohata J, Bruemmer KJ, Chang CJ (2019) Activity-based sensing methods for monitoring the reactive carbon species carbon monoxide and formaldehyde in living systems. Acc Chem Res 52:2841–2848

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  3. Heck H, Casanova M (2004) The implausibility of leukemia induction by formaldehyde: a critical review of the biological evidence on distant-site toxicity. Regul Toxicol Pharmacol 40:92–106

    Article  CAS  PubMed  Google Scholar 

  4. Du P, Ran WG, Li WP, Luo LH, Huang XY (2019) Morphology evolution of Eu3+-activated NaTbF4 nanorods: a highly-efficient near-ultraviolet light-triggered red-emitting platform towards application in white light-emitting diodes. J Mater Chem C 7:10802–10809

    Article  CAS  Google Scholar 

  5. Du P, Cai PQ, Li W.P., Luo, LH, Hou YP, Liu ZG (2019) Ratiometric optical thermometer based on the use of manganese (II)-doped Cs3Cu2I5 thermochromic and fluorescent halides. Microchim Acta 186: 730

  6. Qu J, Xia Q, Ji W, Jing S, Zhu DR, Li L, Huang L, An ZF, Xin CQ, Ni Y, Li M, Jia JD, Song YL, Huang W (2018) A ferrocene∩europium assembly showing phototriggered anticancer activity and fluorescent modality imaging. 47: 1479-1487

  7. El Sayed S, Pascual L, Licchelli M, Martínez-Máñez R, Gil S, Costero AM, Sancenón F (2016) Chromogenic detection of aqueous formaldehyde using functionalized silica nanoparticles. ACS Appl Mater Interfaces 8:14318–14322

    Article  CAS  PubMed  Google Scholar 

  8. Li HJ, Sun X, Xue F, Ou N, Sun BW, Qian DJ, Chen M, Wang D, Yang JH, Wang XY (2018) Redox induced fluorescence on-off switching based on nitrogen enriched graphene quantum dots for formaldehyde detection and bioimaging. ACS Sustain Chem Eng 6:1708–1716

    Article  CAS  Google Scholar 

  9. Lin Q, Fan YQ, Gong GF, Mao PP, Wang J, Guan XW, Liu J, Zhang YM, Yao H, Wei TB (2018) Ultrasensitive detection of formaldehyde in gas and solutions by a catalyst preplaced sensor based on a pillar[5] arene derivative. ACS Sustain Chem Eng 6:8775–8781

    Article  CAS  Google Scholar 

  10. Chaiendoo K, Boonchiangma S, Promarak V, Ngeontae W (2018) New sensitive strategy for formaldehyde sensing by in situ generation of luminescent silver nanoclusters. Colloid Polym Sci 29:1995–2004

    Article  CAS  Google Scholar 

  11. Nandi S, Sharma E, Trivedi V, Biswas S (2018) Metal-organic framework showing selective and sensitive detection of exogenous and endogenous formaldehyde. Inorg Chem 57:15149–15157

    Article  CAS  PubMed  Google Scholar 

  12. Chaiendoo K, Sooksin S, Kulchat S, Promarak V, Tuntulani T, Ngeontae W (2018) A new formaldehyde sensor from silver nanoclusters modified Tollens’ reagent 255:41–48

  13. Tang Y, Kong X, Xu A, Dong B, Lin W (2016) Development of a two-photon fluorescent probe for imaging of endogenous formaldehyde in living tissues. Angew Chem Int Ed 55:3356–3359

    Article  CAS  Google Scholar 

  14. Yang H, Fang G, Guo M, Ning P, Feng Y, Yu H, Meng X (2018) A ratiometric two-photon fluorescent probe for selective detection of endogenous formaldehyde via aza-Cope reaction. Sens Actuators B: Chem 270:318–326

    Article  CAS  Google Scholar 

  15. Cheng X, Xu J, Wang L, Xu GH, Wei FG, Cai YY, Hu Q, Cen Y (2019) A redox modulated ratiometric fluorometric method based on the use of dual-color carbon dots for determination of the activity of enzymes participating in ascorbic acid-related reactions. Microchim Acta 186:818

    Article  CAS  Google Scholar 

  16. Wang J, Qiu Y, Li DQ, Liu XY, Jiang CX, Huang L, Wen HM, Hu J (2019) Ratiometric fluorometric and visual determination of cyanide based on the use of carbon dots and gold nanoclusters. Microchim Acta 186:809

    Article  CAS  Google Scholar 

  17. Liu H, Sun Y, Li Z, Yang J, Aryee AA, Qu L, Du D, Lin Y (2019) Lysosome-targeted carbon dots for ratiometric imaging of formaldehyde in living cells. Nanoscale 11:8458–8463

    Article  CAS  PubMed  Google Scholar 

  18. Chen S, Jia Y, Zou GY, Yu YL, Wang JH (2019) A ratiometric fluorescent nanoprobe based on naphthalimide derivative-functionalized carbon dots for imaging lysosomal formaldehyde in HeLa cells. Nanoscale 11:6377–6383

    Article  CAS  PubMed  Google Scholar 

  19. Patel KD, Singh RK, Kim HW (2019) Carbon-based nanomaterials as an emerging platform for theranostics. Mater Horiz 6:434–469

    Article  CAS  Google Scholar 

  20. Wang ZX, Jin X, Gao YF, Kong FY, Wang WJ, Wang W (2019) Fluorometric and colorimetric determination of hypochlorite using carbon nanodots doped with boron and nitrogen. Microchim Acta 186:328

    Article  CAS  Google Scholar 

  21. Li Y, Lin H, Luo C, Wang Y, Jiang C, Qi R, Huang R, Travas-sejdic J, Peng H (2017) Aggregation induced red shift emission of phosphorus doped carbon dots. RSC Adv 7:32225–32228

    Article  CAS  Google Scholar 

  22. Sun X, Bruckner C, Lei Y (2015) One-pot and ultrafast synthesis of nitrogen and phosphorus co-doped carbon dots possessing bright dual wavelength fluorescence emission. Nanoscale 7:17278–17282

    Article  CAS  PubMed  Google Scholar 

  23. Liu H, Li RS, Zhou J, Huang CZ (2017) Branched polyethylenimine-functionalized carbon dots as sensitive and selective fluorescent probes for N-acetylcysteine via an off-on mechanism. Analyst 142:4221–4227

    Article  CAS  PubMed  Google Scholar 

  24. Zhi B, Gallagher MJ, Frank BP, Lyons TY, Qiu TA, Da J, Mensch AC, Hamers RJ, Rosenzweig Z, Fairbrother DH, Haynes CL (2018) Investigation of phosphorous doping effects on polymeric carbon dots: fluorescence, photostability, and environmental impact. Carbon 129:438–449

    Article  CAS  Google Scholar 

  25. Fu X, Sheng L, Yu Y, Ma M, Cai Z, Huang X (2018) Rapid and universal detection of ovalbumin based on N,O,P-co-doped carbon dots-fluorescence resonance energy transfer technology. Sens Actuators B: Chem 269:278–287

    Article  CAS  Google Scholar 

  26. Wang J, Sheng R, Li H, Zhang Z, Wang N, Zhang Z, Huang CZ (2017) Highly fluorescent carbon dots as selective and visual probes for sensing copper ions in living cells via an electron transfer process. Biosens Bioelectron 97:157–163

    Article  CAS  PubMed  Google Scholar 

  27. 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

    Article  CAS  Google Scholar 

  28. Wei L, Tan W, Wang G, Li Q, Dong F, Guo Z (2019) The antioxidant and antifungal activity of chitosan derivatives bearing Schiff bases and quaternary ammonium salts. Carbohyd polym 226:115256–115266

    Article  CAS  Google Scholar 

  29. Wang YA, Liu T, Zhong GQ (2019) Synthesis, characterization and applications of copper (II) complexes with Schiff bases derived from chitooligosaccharide and iodosubstituted salicylaldehyde. Carbohyd Polym 224:115151–115157

    Article  CAS  Google Scholar 

  30. Jin H, Gui R, Wang Y, Sun J (2017) Carrot-derived carbon dots modified with polyethyleneimine and Nile blue for ratiometric two-photon fluorescence turn-on sensing of sulfide anion in biological fluids. Talanta 169:141–148

    Article  CAS  PubMed  Google Scholar 

  31. Zhou Z, Tian P, Liu X, Mei S, Zhou D, Li D, Jing P, Zhang W, Guo R, Qu S, Rogach AL (2018) Hydrogen peroxide-treated carbon dot phosphor with a bathochromic-shifted, aggregation-enhanced emission for light-emitting devices and visible light communication. Adv Sci 5:1800369–1800378

    Article  CAS  Google Scholar 

  32. Gan Z, Xu H, Hao Y (2016) Mechanism for excitation-dependent photoluminescence from graphene quantum dots and other graphene oxide derivates: consensus, debates and challenges. Nanoscale 8:7794–7807

    Article  CAS  PubMed  Google Scholar 

  33. Chen W, Han J, Wang X, Liu X, Liu F, Wang F, Yu RQ, Jiang JH (2018) Aggregation-induced emission-based fluorescence probe for fast and sensitive imaging of formaldehyde in living cells. ACS Omega 3:14417–14422

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  34. Zhang Y, Yan B (2019) A portable self-calibrating logic detector for gradient detection of formaldehyde based on luminescent metal organic frameworks. J Mater Chem C 7:5652–5657

    Article  CAS  Google Scholar 

  35. Chen HW, Li H, Song QH (2018) BODIPY-substituted hydrazine as a fluorescent probe for rapid and sensitive detection of formaldehyde in aqueous solutions and in live cells. ACS Omega 3:18189–18195

    Article  CAS  Google Scholar 

Download references

Acknowledgments

We gratefully acknowledge the financial support from funding for school-level research projects of Yancheng Institute of Technology (xjr2019021, xjr2019020) and the Natural Science Foundation of Jiangsu Province (BK20191041). This work also was supported by the National Natural Science Foundation of China (Grant No. 21671101).

Author information

Authors and Affiliations

  1. School of Materials Science and Engineering, Yancheng Institute of Technology, Yancheng, 224051, People’s Republic of China

    Jian Qu, Xin Zhang, Yifan Liu, Yichao Xie & Jiawei Cai

  2. School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing, 211816, People’s Republic of China

    Guojin Zha & Su Jing

Authors
  1. Jian Qu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xin Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yifan Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yichao Xie
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jiawei Cai
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Guojin Zha
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Su Jing
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Xin Zhang or Su Jing.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

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

(DOCX 1107 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Qu, J., Zhang, X., Liu, Y. et al. N, P-co-doped carbon dots as a dual-mode colorimetric/ratiometric fluorescent sensor for formaldehyde and cell imaging via an aminal reaction-induced aggregation process. Microchim Acta 187, 355 (2020). https://doi.org/10.1007/s00604-020-04337-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00604-020-04337-0

Keywords

Search

Navigation