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Selective detection of folate and analogs employing highly luminescent manganese-nitrogen co-doped carbon quantum dots: a fluorimetric turn-off strategy

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Abstract

Facile detection of folate and analog by following the luminescence quenching of newly synthesized manganese-nitrogen co-doped carbon dots has been highlighted. Here, we devised, for the first time, water-dispersible manganese-nitrogen co-doped carbon dots from branched polyethyleneimine, manganese chloride, and citrate. The developed quantum dots emit bright blue fluorescence with a quantum yield of ~ 0.37. These show sensitive and selective fluorescence quenching by folates with a low limit of detection. The real samples with folate yield reproducible results, and coexistent molecules other than those belonging to the folate family did not cause any detectable change in the luminescence of quantum dots. Hence, the developed manganese-nitrogen co-doped carbon dots–based sensing strategy can offer a convenient and label-free protocol for the detection and quantification of folates in real samples and microorganisms.

Graphical Abstract

Highly luminescent Mn-, N-CQDs show fluorometric sensitivity toward folic acid in real food sample.

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All the data presented in this paper are complete set and these are not part of any other unpublished work.

Abbreviations

Mn-, N-CQDs:

Manganese-nitrogen co-doped carbon dots

PEI:

Branched polyethyleneimine

PL:

Photoluminescence

Mn:

Manganese

QY:

Quantum yield

CDs:

Carbon dots

FA:

Folate

MTX:

Methotrexate

UA:

Uric acid

Gus:

Guanosine

AA:

L-ascorbic acid

Glu:

Glutathione

Cys:

L-cystine

Try:

Tryptophan

OA:

Oxalic acid

References

  1. Zhang JR, Wang ZL, Qu F, Luo HQ, Li NB (2014) Polyethylenimine-capped silver nanoclusters as a fluorescence probe for highly sensitive detection of folic acid through a two-step electron-transfer process. Journal of Agricultural and Food Chemistry.https://doi.org/10.1021/jf4054534

  2. Xiao F, Ruan C, Liu L, Yan R, Zhao F, Zeng B (2008) Single-walled carbon nanotube-ionic liquid paste electrode for the sensitive voltammetric determination of folic acid. Sens Actuators B: Chem. https://doi.org/10.1016/j.snb.2008.06.037

  3. Maiyalagan T, Sundaramurthy J, Kumar PS, Kannan P, Opallo M, Ramakrishna S (2013) Nanostructured α-Fe2O3 platform for the electrochemical sensing of folic acid. Anal. https://doi.org/10.1039/C3AN00070B

  4. Akbar S, Anwar A, Kanwal Q (2016) Electrochemical determination of folic acid: a short review. Anal Biochem. https://doi.org/10.1016/j.ab.2016.07.002

  5. Chekin F, Teodorescu F, Coffinier Y, Pan GH, Barras A, Boukherroub R, Szunerits S (2016) MoS2/reduced graphene oxide as active hybrid material for the electrochemical detection of folic acid in human serum. Biosens Bioelectron. https://doi.org/10.1016/j.bios.2016.05.095

  6. Pellis L, Dommels Y, Venema D, Polanen A, Lips E, Baykus H, Kok F, Kampman E, Keijer J (2008) High folic acid increases cell turnover and lowers differentiation and iron content in human HT29 colon cancer cells. Bri J Nutr. https://doi.org/10.1017/S0007114507824147

  7. Chen X, Zhu X, Xu Z, Xu M, Wen Y, Liu Y, Lui J, Oin X (2019) Target hexagonal Pdnanosheet combination therapy for rheumatoid arthritis via the photothermal controlled release of MTX. J Mater Chem B. https://doi.org/10.1039/C8TB02302F

  8. Sarkar C, Chowdhuri AR, Kumar A, Laha D, Garai S, Chakraborty J, Sahu SK (2018) One pot synthesis of carbon dots decorated carboxymethyl cellulose-hydroxyapatite nanocomposite for drug delivery, tissue engineering and Fe3+ ion sensing. CarbohydrPolym. https://doi.org/10.1016/j.carbpol.2017.11.091

  9. Chaudhary S, Umar A, Bhasin K, Singh BN (2017) Applications of carbon dots in nanomedicine. J Biomed Nanotechnolhttps://doi.org/10.1166/jbn.2017.2390

  10. Wang TY, Chen CY, Wang CM, Tan YZ, Liao WS (2017) Multicolor functional carbon dots via one-step refluxing synthesis. ACS Sens. https://doi.org/10.1021/acssensors.6b00607

  11. Wang Y, Lu L, Peng H, Xu J, Wang F, Qi R, Xu Z, Zhang W (2016) Multi-doped carbon dots with ratiometric pH sensing properties for monitoring enzyme catalytic reactions. ChemCommun. https://doi.org/10.1039/C6CC02874H

  12. Xu Q, Su R, Chen Y, TheruvakkattilSreenivasan S, Li N, Zheng X, Zhu J, Pan H (2018) Metal charge transfer doped carbon dots with reversibly switchable, ultra-high quantum yield photoluminescence. App Nano Mater. https://doi.org/10.1021/acsanm.8b00277

    Article  CAS  Google Scholar 

  13. Molkenova A, Atabaev T. Phosphorus-doped carbon dots (P-CDs) from dextrose for low-concentration ferric ions sensing in water. Acs Omega. https://doi.org/10.1016/j.ijleo.2019.05.013

  14. Li M, Chen T, Gooding J J, Liu J (2019) Review of carbon and graphene dots for sensing. ACS Sens. https://doi.org/10.1021/acssensors.9b00514

  15. Tajik S, Dourandish Z, Zhang K, Beitollahi H, Le Q V, Jang H W, Shokouhimehr M (2020) RSC Advances. https://doi.org/10.1039/D0RA00799D

  16. Tang M, Ren G, Zhu B, Yu L, Liu X, Chai F, Wu H (2019) Facile synthesis of orange emissive carbon dots and their application for mercury ion detection and fast fingerprint development. Anal Methods. https://doi.org/10.1039/C9AY00178F

  17. Atchudan R, Edison TNJI, Aseer KR, Perumal S, Karthik N, Lee JB (2018) Highly fluorescent nitrogen-doped carbon dots derived from Phyllanthus acidus utilized as a fluorescent probe for label-free selective detection of Fe3+ ions, live cell imaging and fluorescent ink. Biosens Bioelctronics. https://doi.org/10.1016/j.bios.2017.07.076.

  18. Zhang H, Ming H, Lian S, Huang H, Li H, Zhang L, Liu Y, Kang Z (2011) Fe 2 O 3/carbon quantum dots complex photocatalysts and their enhanced photocatalytic activity under visible light. Dalton Trans. https://doi.org/10.1039/C1DT11147G

  19. Guo Y, Zhang J, Zhou D, Dong ML (2018) Fabrication of Ag/CDots/BiOBr ternary photocatalyst with enhanced visible-light driven photocatalytic activity for 4-chlorophenol degradation. J Mol Liq. https://doi.org/10.1016/j.molliq.2018.04.091

  20. Kumari R, Kumar Sahu JC (2018) Synthesis of longer‐wavelength‐emissive carbon quantum dots for WLEDs and investigation of their photoluminescence properties. Chem Sel. https://doi.org/10.1002/slct.201802637

  21. Sun C, Zhang Y, Kalytchuk S, Wang Y, Zhang X, Gao W, Zhao J, Cepe K, Zboril R (2015) Down-conversion monochromatic light-emitting diodes with the color determined by the active layer thickness and concentration of carbon dots. J Mater Chem C. https://doi.org/10.1039/C5TC01379H

  22. Zhou D, Li D, Jing P, Zhai Y, Shen D, Qu S (2017) Conquering aggregation-induced solid-state luminescence quenching of carbon dots through a carbon dots-triggered silica gelation process. Chem Mater. https://doi.org/10.1021/acs.chemmater.6b05375

  23. Liu Q, Li D, Zhu Z, Yu S, Zhang Y, Yu D (2018) N-doped carbon dots from phenol derivatives for excellent colour rendering WLEDs. RSC Adv. https://doi.org/10.1039/C7RA12522D

  24. Ding H, Yu SB, Wei JS (2016) Full-color light-emitting carbon dots with a surface-state-controlled luminescence mechanism. Acs Nano. https://doi.org/10.1021/acsnano.5b05406

  25. Ge J, Jia Q, Liu W, Guo L, Liu Q, Lan M, Zhang H, Meng X. Red‐emissive carbon dots for fluorescent, photoacoustic, and thermal theranostics in living mice. Adv Mater. https://doi.org/10.1002/adma.201500323.

  26. Yang Y, Wang X, Liao G, Liu X, Chen Q, Li H, Lu L, Zhao P. iRGD-decorated red shift emissive carbon nanodots for tumor targeting fluorescence imaging. J Colloid Interface Sci. https://doi.org/10.1016/j.jcis.2017.09.007

  27. Xu Q, Kuang T, Liu Y, Cai L, Peng X, Sreeprasad TS, Yu Z. Heteroatom-doped carbon dots: synthesis, characterization, properties, photoluminescence mechanism and biological applications. J Mater Chem B. https://doi.org/10.1039/C6TB02131J

  28. Feng X, Zhang F, Wang Y, Zhang Y, Yang Y, Liu L. Luminescent carbon quantum dots with high quantum yield as a single white converter for white light emitting diodes. Appl Phys Lett. https://doi.org/10.1063/1.4936234

  29. Hu L, Sun Y,Li S, Wang X, Hu K, Wang L, Liang X (2014) Multifunctional carbon dots with high quantum yield for imaging and gene delivery. Carbon. https://doi.org/10.1016/j.carbon.2013.10.023

  30. Xu Y, Wu M, Liu Y, Feng XZ, Yin XB, He XB. Nitrogen‐doped carbon dots: a facile and general preparation method, photoluminescence investigation, and imaging applications. Chem- A Eur J. https://doi.org/10.1002/chem.201203641

  31. Irmania N, Dehvari K, Gedda G, Tseng PJ (2020) Manganese‐doped green tea‐derived carbon quantum dots as a targeted dual imaging and photodynamic therapy platform. J Biomed Mater Res Part B: Appl Biomater. https://doi.org/10.1002/jbm.b.34508

  32. Bourlinos AB, Trivizas G, Karakassides MA, Baikousi M, Kouloumpis A, Gournis D, Bakandritsos A, Hola K, Kozak O, Zboril R, Papagiannouli I, Aloukos P, Couris S (2015) Green and simple route toward boron doped carbon dots with significantly enhanced non-linear optical properties. Carbon. https://doi.org/10.1016/j.carbon.2014.11.032

  33. Chandra S, Patra P, Pathan SH, Roy S, Mitra S, Layek A, Bhar R , Pramanik P, Goswami B. Luminescent S-doped carbon dots: an emergent architecture for multimodal applications. J Mater Sci B. https://doi.org/10.1039/C3TB00583F

  34. Qian Z, Shan X, Chai L, Ma J, Chen J, Feng H (2014) Si-doped carbon quantum dots: a facile and general preparation strategy, bioimaging application, and multifunctional sensor. ACS Appl Mater Interfaces. https://doi.org/10.1021/am500403n

  35. Prasad KS, Pallela R, Kim DM, Shim P (2013) Microwave‐assisted one‐pot synthesis of metal‐free nitrogen and phosphorus dual‐doped nanocarbon for electrocatalysis and cell imaging. Part PartSyst Charact. https://doi.org/10.1002/ppsc.201300020

  36. Gong Y, Yu B, Yang W, Zhang B (2016) Phosphorus, and nitrogen co-doped carbon dots as a fluorescent probe for real-time measurement of reactive oxygen and nitrogen species inside macrophages. Biosens Bioelectronics. https://doi.org/10.1016/j.bios.2016.01.022

  37. Xu Q, Liu Y, Su R, Cai L, Li B, Zhang Y, Zhang L, Wang Y, Wang Y, Li N (2016) Highly fluorescent Zn-doped carbon dots as Fenton reaction-based bio-sensors: an integrative experimental–theoretical consideration. Nanoscale. https://doi.org/10.1039/C6NR05434J.

  38. Xu Q, Su R, Chen Y, Sreenivasan T S, Li N, Zheng X, Zhu J, Pan H, Li W, Xu C, Xia Z, Dai L. ACS Appl Nano Mater. https://doi.org/10.1021/acsanm.8b00277

  39. Chiu SH, Gedda G, Girma WM, Chen JK, Ling YC, Ghule AV, Ou KL, Chang Y (2016) Rapid fabrication of carbon quantum dots as multifunctional nanovehicles for dual-modal targeted imaging and chemotherapy. ActaBiomater. https://doi.org/10.1016/j.actbio.2016.09.027

  40. Yao Y, Gedda G, Girma WM, Yen CL, Ling YC, Chang J (2017) Magnetofluorescent carbon dots derived from crab shell for targeted dual-modality bioimaging and drug delivery. ACS Appl Mater Interfaces. https://doi.org/10.1021/acsami.7b01599

  41. Mehta SK, Kumar S, Chaudhary S, Bhasin KK (2010) Nucleation and growth of surfactant passivated CdS and HgS nanoparticles: time-dependent absorption and luminescence profiles. Nanoscale. https://doi.org/10.1039/B9NR00070D

  42. Chopra N, Mansingh A, Chadha GK (1990) Electrical, optical and structural properties of amorphous V2O5 TeO2 blown films. J Non-Cryst Solids. https://doi.org/10.1016/0022-3093(90)90819-8

  43. Dong Y, Wan L, Cai J, Fang Q, Chi Y, Chen G (2015) Natural carbon-based dots from humic substances. Scientific Reports. https://doi.org/10.1038/srep10037

  44. Mizuguchi M, Nara M, Kawano K, Nitta K (1997) FT-IR study of the Ca2+-binding to bovine α-lactalbumin: relationships between the type of coordination and characteristics of the bands due to the Asp COO− groups in the Ca2+-binding site. FEBS Lett. https://doi.org/10.1016/S0014-5793(97)01274-X

  45. Zheng M, Zhang H, Gong X, Xu R, Xiao Y, Dong H, Liu X,Liu Y (2013) A simple additive-free approach for the synthesis of uniform manganese monoxide nanorods with large specific surface area. Nanoscale Res Lett. https://doi.org/10.1186/1556-276X-8-166

  46. Alaş MO, Güngör A, Genç R, Erdem E (2019) Feeling the power: robust supercapacitors from nanostructured conductive polymers fostered with Mn2+ and carbon dots. Nanoscale. https://doi.org/10.1039/C9NR03544C

  47. Li JY, Liu Y, Shu QW, Liang JM, Zhang F, Chen XP, Deng XY, Swihart MT, Tan KJ (2017) One-pot hydrothermal synthesis of carbon dots with efficient up- and down-converted photoluminescence for the sensitive detection of morin in a dual-readout assay. Langmuir. https://doi.org/10.1021/acs.langmuir.6b04225

  48. Yang L, Qin A, Chen S, Liao L, Qin J,Zhang K (2018) Manganese(ii) enhanced fluorescent nitrogen-doped graphene quantum dots: a facile and efficient synthesis and their applications for bioimaging and detection of Hg2+ ions. RSC Adv. https://doi.org/10.1039/C7RA12133D

  49. Jin X, Sun X, Chen G, Ding L, Li Y, Liu Z, Wang Z, Pan W, Hu C, Wang J, pH-sensitive carbon dots for the visualization of regulation of intracellular pH inside living pathogenic fungal cells. Carbon. https://doi.org/10.1016/j.carbon.2014.09.071

  50. Gostynski R, Conradie J Erasmus E (2017) Significance of the electron-density of molecular fragments on the properties of manganese (iii) β-diketonato complexes: an XPS and DFT study. RSC Advances. https://doi.org/10.1039/C7RA04921H.

  51. Ma Y, Chen Y, Liu J, Han Y, Ma S, Chen X (2018) Ratiometric fluorescent detection of chromium(VI) in real samples based on dual emissive carbon dots. Talanta. https://doi.org/10.1016/j.talanta.2018.03.081

  52. Zhang HY, Wang Y, Xiao S, Wang H, Wang JH, Feng L (2017) Rapid detection of Cr(VI) ions based on cobalt(II)-doped carbon dots. BiosensBioelectron. https://doi.org/10.1016/j.bios.2016.08.010

  53. Wu W, Zhan L, Fan W, Song J, Li X , Li Z, Wang R, Zhang J, Zheng J, Wu M, Zeng H (2015) Cu-N dopants boost electron transfer and photooxidation reactions of carbon dots. AngewChem. https://doi.org/10.1002/anie.201501912

  54. Tadesse A, Hagos M, RamaDevi D, Basavaiah K, Belachew N (2020) Fluorescent-nitrogen-doped carbon quantum dots derived from citrus lemon juice: green synthesis, mercury(II) ion sensing, and live cell imaging. ACS Omega. https://doi.org/10.1021/acsomega.9b03175

  55. Kayal S, Halder M (2019) A ZnS quantum dot-based super selective fluorescent chemosensor for soluble ppb-level total arsenic [As(iii) + As(v)] in aqueous media: direct assay utilizing aggregation-enhanced emission (AEE) for analytical application. Anal. https://doi.org/10.1039/C9AN00516A

  56. Chu HW, Unnikrishnan B, Anand A, Lin YW, Huang CC (2020) Carbon quantum dots for the detection of antibiotics and pesticides. Journal of food and drug analysis. https://doi.org/10.38212/2224-6614.1269

  57. Zhao Y, Zou S, Huo D, Hou C, Yang M, Li J, Bian M (2019) Simple and sensitive fluorescence sensor for methotrexate detection based on the inner filter effect of N, S co-doped carbon quantum dots. Anal ChimActa. https://doi.org/10.1016/j.aca.2018.10.005

  58. Li X, Wu X, Zhang F, Zhao B, Li Y (2019) Label-free detection of folic acid using a sensitive fluorescent probe based on ovalbumin stabilized copper nanocluster,Talanta. https://doi.org/10.1016/j.talanta.2018.11.067

  59. Chen S, Yu YL, Wang JH (2018) Inner filter effect-based fluorescent sensing systems: a review, Anal ChimActa. https://doi.org/10.1016/j.aca.2017.10.026

  60. Jhonsi MA, Thulasi S, Kathiravan A. Impact of capping agent on the electron transfer dynamics of CdTe QDs with methyl viologen. J Lumin. https://doi.org/10.1016/j.jlumin.2016.06.022

  61. An J, Gou Y, Yang C, Hu F, Wang C (2013) Synthesis of a biocompatible gelatin functionalized graphene nanosheets and its application for drug delivery. Mater SciEng: C. https://doi.org/10.1016/j.msec.2013.03.008

  62. Khodadadei F, Safarian S, Ghanbari N (2017) Methotrexate-loaded nitrogen-doped graphene quantum dots nanocarriers as an efficient anticancer drug delivery system. Mater Sci Eng: C. https://doi.org/10.1016/j.msec.2017.05.049

  63. Arsalani N, Mokhtari PN, Jabbari E (2019) Microwave-assisted and one-step synthesis of PEG passivated fluorescent carbon dots from gelatin as an efficient nanocarrier for methotrexate delivery. Artificial Cells, Nanomedicine, and Biotechnology. https://doi.org/10.1080/21691401.2018.1562460

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Acknowledgements

M. H. thanks IIT Kharagpur for financial support. H.S. thanks DST-INSPIRE for his fellowship. We thank Prof. N. Sarkar for help in DLS experiments and also Prof. N. D. Pradeep Singh for HPLC measurements.

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  1. Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur, 721302, India

    Harish Singh & Mintu Halder

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Singh, H., Halder, M. Selective detection of folate and analogs employing highly luminescent manganese-nitrogen co-doped carbon quantum dots: a fluorimetric turn-off strategy. J Nanopart Res 25, 92 (2023). https://doi.org/10.1007/s11051-023-05721-6

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