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Hydrothermal synthesis of N, P co-doped graphene quantum dots for high-performance Fe3+ detection and bioimaging

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Abstract

Doped carbon-based materials have attracted considerable attentions due to their extraordinary optical, thermal, and electronic properties. Herein, we demonstrate a facile and universal approach, which involves the hydrothermal treatment of citric acid and phosphonitrilic chloride trimer (Cl6N3P3), for the production of nitrogen and phosphorus co-doped graphene quantum dots (N, P-GQDs). The obtained N, P-GQDs with a mean size of about 3.4 nm exhibit bright yellow fluorescence, good-solubility, and attractive optical stability. Although the quantum yield as high as 34.8% has been proved in our synthesized N, P-GQDs, the fluorescence can be also fleetly and selectively quenched by Fe3+ ions. Therefore, high-performance Fe3+ sensors are fabricated with N, P-GQDs, with an ultra-sensitive detection limit of 146 nM. Furthermore, high ionic strength, mild acids, and alkaline are demonstrated to have a small impact on the fluorescence intensity of the N, P-GQDs. Finally, the as-synthesized N, P-GQDs, with bright luminescence and excellent biocompatibility, are applied for bioimaging, e.g., fibroblast cells.

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References

  • Atchudan R, Edison T, Aseer KR, Perumal S, Karthik N, Lee YR (2018a) 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. Bioelectron. 99:303–311

    Article  CAS  Google Scholar 

  • Atchudan R, Jebakumar Immanuel Edison TN, Perumal S, Lee YR (2018b) Indian gooseberry-derived tunable fluorescent carbon dots as a promise for in vitro/in vivo multicolor bioimaging and fluorescent ink. ACS Omega. 3(12):17590–17601

    Article  CAS  Google Scholar 

  • Chang KE, Kim C, Yoo TJ, Kwon MG, Heo S, Kim SY, Hyun Y, Yoo JI, Ko HC, Lee BH (2019) High responsivity near infrared photodetector using gate modulated graphene/germanium schottky junction. Adv. Electron. Mater. 5(6)

  • Chen L, Yang G, Wu P, Cai C (2017) Real-time fluorescence assay of alkaline phosphatase in living cells using boron-doped graphene quantum dots as fluorophores. Biosens. Bioelectron. 96:294–299

    Article  CAS  Google Scholar 

  • Chen W, Li D, Tian L, Xiang W, Wang T, Hu W, Hu Y, Chen S, Chen J, Dai Z (2018) Synthesis of graphene quantum dots from natural polymer starch for cell imaging. Green Chem. 20(19):4438–4442

    Article  CAS  Google Scholar 

  • Dutta Chowdhury A, Doong RA (2016) Highly sensitive and selective detection of nanomolar ferric ions using dopamine functionalized graphene quantum dots. ACS Appl. Mater. Interfaces 8(32):21002–210010

    Article  CAS  Google Scholar 

  • Fu Y, Gao G, Zhi J (2019) Electrochemical synthesis of multicolor fluorescent N-doped graphene quantum dots as a ferric ion sensor and their application in bioimaging. Journal of Materials Chemistry B. 7(9):1494–1502

    Article  CAS  Google Scholar 

  • Gao G, Jiang Y-W, Jia H-R, Yang J, Wu F-G (2018) On-off-on fluorescent nanosensor for Fe3+ detection and cancer/normal cell differentiation via silicon-doped carbon quantum dots. Carbon 134:232–243

    Article  CAS  Google Scholar 

  • Gong X, Ding X, Jiang N, Zhong T, Wang G (2020) Benzothiazole-based fluorescence chemosensors for rapid recognition and “turn-off” fluorescence detection of Fe3+ ions in aqueous solution and in living cells. Microchem. J. 152:104351

    Article  CAS  Google Scholar 

  • Hai X, Guo Z, Lin X, Chen X, Wang J (2018) Fluorescent TPA@GQDs probe for sensitive assay and quantitative imaging of hydroxyl radicals in living cells. ACS Appl. Mater. Interfaces 10(6):5853–5861

    Article  CAS  Google Scholar 

  • Haider G, Roy P, Chiang C-W, Tan W-C, Liou Y-R, Chang H-T, Liang C-T, Shih W-H, Chen Y-F (2016) Electrical-polarization-induced ultrahigh responsivity photodetectors based on graphene and graphene quantum dots. Adv. Funct. Mater. 26(4):620–628

    Article  CAS  Google Scholar 

  • Jia J, Lin B, Gao Y, Jiao Y, Li L, Dong C, Shuang S (2019) Highly luminescent N-doped carbon dots from black soya beans for free radical scavenging, Fe3+ sensing and cellular imaging. Spectrochim. Acta. A Mol. Biomol. Spectrosc. 211:363–372

    Article  CAS  Google Scholar 

  • Kagit R, Yildirim M, Ozay O, Yesilot S, Ozay H (2014) Phosphazene based multicentered naked-eye fluorescent sensor with high selectivity for Fe3+ ions. Inorg. Chem. 53(4):2144–2151

    Article  CAS  Google Scholar 

  • Kaur M, Kaur M, Sharma VK (2018) Nitrogen-doped graphene and graphene quantum dots: a review onsynthesis and applications in energy, sensors and environment. Adv. Colloid Interface Sci. 259:44–64

    Article  CAS  Google Scholar 

  • Khojasteh H, Amiri M, Sohrabi A, Khanahmadzadeh S, Salavati-Niasari M, Moayedi H (2020) Synthesis of magnetically reusable Fe3O4/TiO2-N, P co-doped graphene quantum dot nancomposites using hexachlorocyclophosphazene; high photoluminance property and photocatalytic promoter. J. Mater. Res. Technol. 9(2):1380–1388

    Article  CAS  Google Scholar 

  • Li Y, Shu H, Wang S, Wang J (2015a) Electronic and optical properties of graphene quantum dots: the role of many-body effects. J. Phys. Chem. C 119(9):4983–4989

    Article  CAS  Google Scholar 

  • Li H, Shao F-Q, Zou S-Y, Yang Q-J, Huang H, Feng J-J, Wang A-J (2015b) Microwave-assisted synthesis of N,P-doped carbon dots for fluorescent cell imaging. Microchim. Acta 183(2):821–826

    Article  Google Scholar 

  • Liu Y, Duan W, Song W, Liu J, Ren C, Wu J, Liu D, Chen H (2017a) Red emission B, N, S-co-doped carbon dots for colorimetric and fluorescent dual mode detection of Fe3+ ions in complex biological fluids and living cells. ACS Appl. Mater. Interfaces 9(14):12663–12672

    Article  CAS  Google Scholar 

  • Liu R, Zhao J, Huang Z, Zhang L, Zou M, Shi B, Zhao S (2017b) Nitrogen and phosphorus co-doped graphene quantum dots as a nano-sensor for highly sensitive and selective imaging detection of nitrite in live cell. Sens Actuators B Chem. 240:604–612

    Article  CAS  Google Scholar 

  • Liu Y, Zhao C, Zhao X, Liu H, Wang Y, Du Y, Wei D (2020) A selective N,N-dithenoyl-rhodamine based fluorescent probe for Fe3+ detection in aqueous and living cells. J. Environ. Sci. 90:180–188

    Article  Google Scholar 

  • Lu W, Gong X, Nan M, Liu Y, Shuang S, Dong C (2015) Comparative study for N and S doped carbon dots: Synthesis, characterization and applications for Fe3+ probe and cellular imaging. Anal Chim Acta. 898:116–127

    Article  CAS  Google Scholar 

  • Luo Z, Qi G, Chen K, Zou M, Yuwen L, Zhang X, Huang W, Wang L (2016) Microwave-assisted preparation of white fluorescent graphene quantum dots as a novel phosphor for enhanced white-light-emitting diodes. Adv. Funct. Mater. 26(16):2739–2744

    Article  CAS  Google Scholar 

  • Ma Y, Chen AY, Huang YY, He X, Xie XF, He B, Yang JH, Wang XY (2020) Off-on fluorescent switching of boron-doped carbon quantum dots for ultrasensitive sensing of catechol and glutathione. Carbon 162:234–244

    Article  CAS  Google Scholar 

  • Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV, Grigorieva IV, Firsov AA (2004) Electric field effect in atomically thin carbon films. Science. 306(5696):666–669

    Article  CAS  Google Scholar 

  • Pu ZF, Wen QL, Yang YJ, Cui XM, Ling J, Liu P, Cao QE (2020) Fluorescent carbon quantum dots synthesized using phenylalanine and citric acid for selective detection of Fe3+ ions. Spectrochim Acta A Mol Biomol Spectrosc. 229:117944

    Article  CAS  Google Scholar 

  • Qu D, Zheng M, Du P, Zhou Y, Zhang L, Li D, Tan H, Zhao Z, Xie Z, Sun Z (2013) Highly luminescent S, N co-doped graphene quantum dots with broad visible absorption bands for visible light photocatalysts. Nanoscale 5(24)

  • Shi B, Su Y, Zhang L, Huang M, Liu R, Zhao S (2016) Nitrogen and phosphorus co-doped carbon nanodots as a novel fluorescent probe for highly sensitive detection of Fe3+ in human serum and living cells. ACS Appl. Mater. Interfaces 8(17):10717–10725

    Article  CAS  Google Scholar 

  • Sim Y, Kim SJ, Janani G, Chae Y, Surendran S, Kim H, Yoo S, Seok DC, Jung YH, Jeon C, Moon J, Sim U (2020) The synergistic effect of nitrogen and fluorine co-doping in graphene quantum dot catalysts for full water splitting and supercapacitor. Appl. Surf. Sci. 507:145157

    Article  CAS  Google Scholar 

  • 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(41):17278–17282

    Article  CAS  Google Scholar 

  • Wang D, Wang L, Dong X, Shi Z, Jin J (2012) Chemically tailoring graphene oxides into fluorescent nanosheets for Fe3+ ion detection. Carbon 50(6):2147–2154

    Article  CAS  Google Scholar 

  • Wang L, Li W, Wu B, Li Z, Wang S, Liu Y, Pan D, Wu M (2016) Facile synthesis of fluorescent graphene quantum dots from coffee grounds for bioimaging and sensing. Chem. Eng. J. 300:75–82

    Article  CAS  Google Scholar 

  • Wang Z, Liu Z, Gu B, Gao B, Wang T, Zheng X, Wang G, Guo Q, Chen D (2020a) Ultraviolet light-driven controllable doping of graphene quantum dots with tunable emission wavelength for fluorescence bio-imaging. Mater. Lett. 266:127468

    Article  CAS  Google Scholar 

  • Wang Z, Chen D, Gu B, Gao B, Liu Z, Yang Y, Guo Q, Zheng X, Wang G (2020b) Yellow emissive nitrogen-doped graphene quantum dots as a label-free fluorescent probe for Fe3+ sensing and bioimaging. Diam. Relat. Mater. 104:107749

    Article  CAS  Google Scholar 

  • Xu A, He P, Huang T, Li J, Hu X, Xiang P, Chen D, Yang S, Wang G, Ding G (2018a) Selective supramolecular interaction of ethylenediamine functionalized graphene quantum dots: ultra-sensitive photoluminescence detection for nickel ion in vitro. Synth. Met. 244:106–112

    Article  CAS  Google Scholar 

  • Xu Q, Li B, Ye Y, Cai W, Li W, Yang C, Chen Y, Xu M, Li N, Zheng X, Street J, Luo Y, Cai L (2018b) Synthesis, mechanical investigation, and application of nitrogen and phosphorus co-doped carbon dots with a high photoluminescent quantum yield. Nano Res. 11(7):3691–3701

    Article  CAS  Google Scholar 

  • Yan Y, Liu JH, Li RS, Li YF, Huang CZ, Zhen SJ (2019) Carbon dots synthesized at room temperature for detection of tetracycline hydrochloride. Anal. Chim. Acta 1063:144–151

    Article  CAS  Google Scholar 

  • Yang C-B, Jiang C-B, Zhang M-Y, Chen X, Zou P, Yang R-W, Rao H-B, Wang G-T (2020) A multifunctional Eu-based coordination polymer luminescent sensor for highly sensitive and selective detection of Fe3+ and acetone. Polyhedron 175:114216

    Article  CAS  Google Scholar 

  • Yuan F, Ding L, Li Y, Li X, Fan L, Zhou S, Fang D, Yang S (2015) Multicolor fluorescent graphene quantum dots colorimetrically responsive to all-pH and a wide temperature range. Nanoscale 7(27):11727–11733

    Article  CAS  Google Scholar 

  • Zeng Z, Chen S, Tan TTY, Xiao F-X (2018) Graphene quantum dots (GQDs) and its derivatives for multifarious photocatalysis and photoelectrocatalysis. Catal. Today 315:171–183

    Article  CAS  Google Scholar 

  • Zhang F, Liu F, Wang C, Xin X, Liu J, Guo S, Zhang J (2016) Effect of lateral size of graphene quantum dots on their properties and application. ACS Appl. Mater. Interfaces 8(3):2104–2110

    Article  CAS  Google Scholar 

  • Zhang M, Su R, Zhong J, Fei L, Cai W, Guan Q, Li W, Li N, Chen Y, Cai L, Xu Q (2019) Red/orange dual-emissive carbon dots for pH sensing and cell imaging. Nano Res. 12(4):815–821

    Article  CAS  Google Scholar 

  • Zhao J, Tang L, Xiang J, Ji R, Yuan J, Zhao J, Yu R, Tai Y, Song L (2014) Chlorine doped graphene quantum dots: preparation, properties, and photovoltaic detectors. Appl. Phys. Lett. 105(11)

  • Zhu C, Yang S, Wang G, Mo R, He P, Sun J, Di Z, Yuan N, Ding J, Ding G, Xie X (2015) Negative induction effect of graphite N on graphene quantum dots: tunable band gap photoluminescence. J. Mater. Chem. C 3(34):8810–8816

    Article  CAS  Google Scholar 

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Funding

This work was supported by projects from the National Natural Science Foundation of China under grant nos. 11704204, 61604084, and 51802337; K. C. Wong Magna Fund in Ningbo University; and the Natural Science Foundation of Ningbo under grant no. 2017A610104.

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Correspondence to Da Chen, Qinglei Guo or Gang Wang.

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Yang, Y., Gu, B., Liu, Z. et al. Hydrothermal synthesis of N, P co-doped graphene quantum dots for high-performance Fe3+ detection and bioimaging. J Nanopart Res 23, 40 (2021). https://doi.org/10.1007/s11051-021-05154-z

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