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One-pot synthesis of graphene quantum dots using humic acid and its application for copper (II) ion detection

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Abstract

A new carbon source, humic acid, has been used in fabricating graphene quantum dots by a facial one-pot hydrothermal reaction. The morphology of the cyan emission graphene quantum dots has been characterized by high-resolution transmission electron microscopy (HRTEM). The result showed well-displayed crystalline with a lattice spacing of 0.286 nm. X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR) have demonstrated the diverse functional groups on GQDs, like carboxylic groups, which will cause significant fluorescence quenching by Cu2+ because of the strong chelating interactions. The optical properties of GQDs were characterized by photoluminescence (PL) spectra and ultraviolet–visible (UV–Vis) spectroscopy; it showed that GQDs have an excitation-dependent fluorescence behavior and a large stoke shift with maximum excitation/emission wavelength at 360/470 nm. Furthermore, GQDs showed a good photostability by the kinetic analysis of irradiation for 1500 s and a relatively high quantum yield of 20%, which could be applied in bioimaging. Besides, the selectivity study of metal ions indicates that the GQDs could be used in Cu2+ detection. The linear range is from 1 to 40 μM with the limit of detection (LOD) of 0.44 μM. Overall, this work provided a simple method to produce GQDs with low-cost raw material humic acid, which could be also used in Cu2+ monitoring in river water.

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References

  1. Zhu C, Yang G, Li H, DuLin DYJ (2015) Electrochemical sensors and biosensors based on nanomaterials and nanostructures. Anal Chem 87:230–249. https://doi.org/10.1021/ac5039863

    Article  CAS  Google Scholar 

  2. Hong G, Diao S, Antaris AL, Dai HJCr, (2015) Carbon nanomaterials for biological imaging and nanomedicinal therapy. Chem Rev 115:10816–10906. https://doi.org/10.1021/acs.chemrev.5b00008

    Article  CAS  Google Scholar 

  3. Liang H, Zhang X-B, Lv Y, Gong L, Wang R, Zhu X, Yang R, Tan W (2014) Functional DNA-containing nanomaterials: cellular applications in biosensing, imaging, and targeted therapy. Chem Rev 47:1891–1901. https://doi.org/10.1021/ar500078f

    Article  CAS  Google Scholar 

  4. Chen J, Wu X, Hou X, Su X, Chu Q, Fahruddin N, Zhao JX (2014) Shape-tunable hollow silica nanomaterials based on a soft-templating method and their application as a drug carrier. ACS Appl Mater Int 6:21921–21930. https://doi.org/10.1021/am507642t

    Article  CAS  Google Scholar 

  5. Kimmel DW, LeBlanc G, Meschievitz ME, Cliffel DE (2012) Electrochemical sensors and biosensors. Anal Chem 84(2):685–707. https://doi.org/10.1021/ac202878q

    Article  CAS  Google Scholar 

  6. Shi J, Votruba AR, Farokhzad OC, Langer R (2010) Nanotechnology in drug delivery and tissue engineering: from discovery to applications. Nano Lett 10(9):3223–3230. https://doi.org/10.1021/nl102184c

    Article  CAS  Google Scholar 

  7. Blum AP, Kammeyer JK, Rush AM, Callmann CE, Hahn ME, Gianneschi NC (2015) Stimuli-responsive nanomaterials for biomedical applications. J Am Chem Soc 137(6):2140–2154. https://doi.org/10.1021/ja510147n

    Article  CAS  Google Scholar 

  8. Taylor-Pashow KML, Della Rocca J, Huxford RC, Lin W (2010) Hybrid nanomaterials for biomedical applications. Chem Commun 46(32):5832–5849. https://doi.org/10.1039/C002073G

    Article  CAS  Google Scholar 

  9. Wang J, Ma Q, Wang Y, Shen H, Yuan QJN (2017) Recent progress in biomedical applications of persistent luminescence nanoparticles. Nanoscale 9(19):6204–6218. https://doi.org/10.1039/C7NR01488K

    Article  CAS  Google Scholar 

  10. Mader HS, Kele P, Saleh SM, Wolfbeis OS (2010) Upconverting luminescent nanoparticles for use in bioconjugation and bioimaging. Curr Opin Chem Biol 14:582–596. https://doi.org/10.1016/j.cbpa.2010.08.014

    Article  CAS  Google Scholar 

  11. Zhou C, Yang S, Liu J, Yu M, Zheng JJEB (2013) Luminescent gold nanoparticles: a new class of nanoprobes for biomedical imaging. Exp Biol Med 238:1199–1209. https://doi.org/10.1177/1535370213505825

    Article  CAS  Google Scholar 

  12. Wang F, Tan WB, Zhang Y, Fan X, Wang MJN (2005) Luminescent nanomaterials for biological labelling. Nanotechnology 17(1):R1–R13. https://doi.org/10.1088/0957-4484/17/1/r01

    Article  Google Scholar 

  13. Tang F, Wang C, Wang J, Wang X, Li L (2014) Fluorescent organic nanoparticles with enhanced fluorescence by self-aggregation and their application to cellular imaging. ACS Appl Mater Int 6:18337–18343. https://doi.org/10.1021/am505776a

    Article  CAS  Google Scholar 

  14. Feldmann CJN (2011) Luminescent nanomaterials. Nanoscale 3:1947–1948. https://doi.org/10.1039/C1NR90008K

    Article  CAS  Google Scholar 

  15. Yao C, Tong Y (2012) Lanthanide ion-based luminescent nanomaterials for bioimaging. Trends Anal Chem 39:60–71. https://doi.org/10.1016/j.trac.2012.07.007

    Article  CAS  Google Scholar 

  16. Lin C-AJ, Yang T-Y, Lee C-H, Huang SH, Sperling RA, Zanella M, Li JK, Shen J-L, Wang H-H, Yeh H-I (2009) Synthesis, characterization, and bioconjugation of fluorescent gold nanoclusters toward biological labeling applications. ACS Nano 3:395–401. https://doi.org/10.1021/nn800632j

    Article  CAS  Google Scholar 

  17. Zhang M, Bai L, Shang W, Xie W, Ma H, Fu Y, Fang D, Sun H, Fan L, Han M (2012) Facile synthesis of water-soluble, highly fluorescent graphene quantum dots as a robust biological label for stem cells. J Mater Chem 22:7461–7467. https://doi.org/10.1039/C2JM16835A

    Article  CAS  Google Scholar 

  18. Feng J, Shan G, Maquieira A, Koivunen ME, Guo B, Hammock BD, Kennedy IMJAC (2003) Functionalized europium oxide nanoparticles used as a fluorescent label in an immunoassay for atrazine. Anal Chem 75:5282–5286. https://doi.org/10.1021/ac034063m

    Article  CAS  Google Scholar 

  19. Luo S, Zhang E, Su Y, Cheng T, Shi CJB (2011) A review of NIR dyes in cancer targeting and imaging. Biomaterials 32:7127–7138. https://doi.org/10.1016/j.biomaterials.2011.06.024

    Article  CAS  Google Scholar 

  20. Resch-Genger U, Grabolle M, Cavaliere-Jaricot S, Nitschke R, Nann T (2008) Quantum dots versus organic dyes as fluorescent labels. Nat Methods 5:763. https://doi.org/10.1038/nmeth.1248

    Article  CAS  Google Scholar 

  21. Kim S, Fisher B, Eisler H-J, Bawendi M (2003) Type-II quantum dots: CdTe/CdSe (core/shell) and CdSe/ZnTe (core/shell) heterostructures. J Am Chem Soc 125:11466–11467. https://doi.org/10.1021/ja0361749

    Article  CAS  Google Scholar 

  22. Lovrić J, Bazzi HS, Cuie Y, Fortin GR, Winnik FM, Maysinger D (2005) Differences in subcellular distribution and toxicity of green and red emitting CdTe quantum dots. J Mol Med 83:377–385. https://doi.org/10.1007/s00109-004-0629-x

    Article  Google Scholar 

  23. Wuister SF, Swart I, van Driel F, Hickey SG, de MelloDonegá C (2003) Highly luminescent water-soluble CdTe quantum dots. Nano Lett 3:503–507. https://doi.org/10.1021/nl034054t

    Article  CAS  Google Scholar 

  24. Michalet X, Pinaud FF, Bentolila LA, Tsay JM, Doose S, Li JJ, Sundaresan G, Wu A, Gambhir S, Weiss S (2005) Quantum dots for live cells, in vivo imaging, and diagnostics. Science 307:538–544. https://doi.org/10.1126/science.1104274

    Article  CAS  Google Scholar 

  25. Derfus AM, Chan WC, Bhatia S (2004) Probing the cytotoxicity of semiconductor quantum dots. Nano Lett 4:11–18. https://doi.org/10.1021/nl0347334

    Article  CAS  Google Scholar 

  26. Liang J, He Z, Zhang S, Huang S, Ai X, Yang H, Han HJT (2007) Study on DNA damage induced by CdSe quantum dots using nucleic acid molecular “light switches” as probe. Talanta 71:1675–1678. https://doi.org/10.1016/j.talanta.2006.07.048

    Article  CAS  Google Scholar 

  27. Liu W, Howarth M, Greytak AB, Zheng Y, Nocera DG, Ting AY, Bawendi MG (2008) Compact biocompatible quantum dots functionalized for cellular imaging. J Am Chem Soc 130:1274–1284. https://doi.org/10.1021/ja076069p

    Article  CAS  Google Scholar 

  28. Tan X, Li Y, Li X, Zhou S, Fan L, Yang SJCC (2015) Electrochemical synthesis of small-sized red fluorescent graphene quantum dots as a bioimaging platform. Chem Commun 51:2544–2546. https://doi.org/10.1039/C4CC09332A

    Article  CAS  Google Scholar 

  29. Shao T, Wang G, An X, Zhuo S, Xia Y, Zhu CJRA (2014) A reformative oxidation strategy using high concentration nitric acid for enhancing the emission performance of graphene quantum dots. RSC Adv 4:47977–47981. https://doi.org/10.1039/C4RA06935H

    Article  CAS  Google Scholar 

  30. Yao J, Larson DR, Vishwasrao HD, Zipfel WR, Webb WW (2005) Blinking and nonradiant dark fraction of water-soluble quantum dots in aqueous solution. Proc Natl Acad Sci USA 102(40):14284. https://doi.org/10.1073/pnas.0506523102

    Article  CAS  Google Scholar 

  31. Li L, Wu G, Yang G, Peng J, Zhao J, Zhu J-JJN (2013) Focusing on luminescent graphene quantum dots: current status and future perspectives. Nanoscale 5:4015–4039. https://doi.org/10.1039/C3NR33849E

    Article  CAS  Google Scholar 

  32. Tang L, Ji R, Li X, Bai G, Liu CP, Hao J, Lin J, Jiang H, Teng KS, Yang Z (2014) Deep ultraviolet to near-infrared emission and photoresponse in layered N-doped graphene quantum dots. ACS Nano 8:6312–6320. https://doi.org/10.1021/nn501796r

    Article  CAS  Google Scholar 

  33. Xuan Y, Zhang R-Y, Zhang X-S, An J, Cheng K, Li C, Hou X-L, Zhao Y-DJN (2018) Targeting N-doped graphene quantum dot with high photothermal conversion efficiency for dual-mode imaging and therapy in vitro. Nanotech 29:355101. https://doi.org/10.1088/1361-6528/aacad0

    Article  CAS  Google Scholar 

  34. Ge J, Lan M, Zhou B, Liu W, Guo L, Wang H, Jia Q, Niu G, Huang X, Zhou H (2014) A graphene quantum dot photodynamic therapy agent with high singlet oxygen generation. Nat Commun 5:1–8. https://doi.org/10.1038/ncomms5596

    Article  CAS  Google Scholar 

  35. Schroer ZS, Wu Y, Xing Y, Wu X, Liu X, Wang X, Pino OG, Zhou C, Combs C, Pu QJAANM (2019) Nitrogen–sulfur-doped graphene quantum dots with metal ion-resistance for bioimaging. ACS Appl Nano Mater 2:6858–6865. https://doi.org/10.1021/acsanm.9b01309

    Article  CAS  Google Scholar 

  36. Qu D, Sun Z, Zheng M, Li J, Zhang Y, Zhang G, Zhao H, Liu X, Xie Z (2015) Three colors emission from S, N Co-doped graphene quantum dots for visible light H2 production and bioimaging. Adv Opt Mater 3(3):360–367. https://doi.org/10.1002/adom.201400549

    Article  CAS  Google Scholar 

  37. Novak J, Kozler J, Janoš P, Čežíková J, Tokarová V, Madronová L (2001) Humic acids from coals of the North-Bohemian coal field: I. preparation and characterisation. React Funct Polym 47:101–109. https://doi.org/10.1016/S1381-5148(00)00076-6

    Article  CAS  Google Scholar 

  38. Dong Y, Wan L, Cai J, Fang Q, Chi Y, Chen G (2015) Natural carbon-based dots from humic substances. Sci Rep 5(1):10037. https://doi.org/10.1038/srep10037

    Article  CAS  Google Scholar 

  39. R. W. Youngs and C. M. Frost (1963) Proceedings of the North Dakota Academy of Science. http://ashipunov.me/journals/pndas/pndas_1963.pdf.Accessed 24 October 2020

  40. Ikeya K, Sleighter RL, Hatcher PG, Watanabe A (2015) Characterization of the chemical composition of soil humic acids using fourier transform ion cyclotron resonance mass spectrometry. Geochim Cosmochim Acta 153:169–182. https://doi.org/10.1016/j.gca.2015.01.002

    Article  CAS  Google Scholar 

  41. Shi W, Fan H, Ai S, Zhu L (2015) Preparation of fluorescent graphene quantum dots from humic acid for bioimaging application. New J Chem 39:7054–7059. https://doi.org/10.1039/C5NJ00760G

    Article  CAS  Google Scholar 

  42. Piccolo A, Spaccini R, Drosos M, Vinci G, Cozzolino V (2018) The molecular composition of humus carbon: recalcitrance and reactivity in soils. The future of soil carbon, 1st edn. Elsevier Academic Press, Cambridge, pp 87–124

    Google Scholar 

  43. Dong Y, Chen C, Zheng X, Gao L, Cui Z, Yang H, Guo C, Chi Y, Li CM (2012) One-step and high yield simultaneous preparation of single- and multi-layer graphene quantum dots from CX-72 carbon black. J Mater Chem 22(18):8764–8766. https://doi.org/10.1039/C2JM30658A

    Article  CAS  Google Scholar 

  44. Pan D, Zhang J, Li Z, Wu M (2010) Hydrothermal route for cutting graphene sheets into blue-luminescent graphene quantum dots. Adv Mater 22(6):734–738. https://doi.org/10.1002/adma.200902825

    Article  CAS  Google Scholar 

  45. Li L-L, Ji J, Fei R, Wang C-Z, Lu Q, Zhang J-R, Jiang L-P, Zhu J-J (2012) A facile microwave avenue to electrochemiluminescent two-color graphene quantum dots. Adv Func Mater 22(14):2971–2979. https://doi.org/10.1002/adfm.201200166

    Article  CAS  Google Scholar 

  46. Zhu S, Zhang J, Liu X, Li B, Wang X, Tang S, Meng Q, Li Y, Shi C, Hu R, Yang B (2012) Graphene quantum dots with controllable surface oxidation, tunable fluorescence and up-conversion emission. RSC Adv 2(7):2717–2720. https://doi.org/10.1039/C2RA20182H

    Article  CAS  Google Scholar 

  47. Tang L, Ji R, Li X, Teng KS, Lau SP (2013) Size-dependent structural and optical characteristics of glucose-derived graphene quantum dots. Part Part Syst Charact 30(6):523–531. https://doi.org/10.1002/ppsc.201200131

    Article  CAS  Google Scholar 

  48. Hong G-L, Zhao H-L, Deng H-H, Yang H-J, Peng H-P, Liu Y-H, Chen W (2018) Fabrication of ultra-small monolayer graphene quantum dots by pyrolysis of trisodium citrate for fluorescent cell imaging. Int J Nanomed 13:4807–4815. https://doi.org/10.2147/IJN.S168570

    Article  CAS  Google Scholar 

  49. Obeng Y (2009) Graphene and emerging materials for post-CMOS applications ECS transactions. Electrochemical Society, Pennington

    Google Scholar 

  50. Matsuura D, Kizuka T (2012) Structures of graphene/cobalt interfaces in cobalt-encapsulated carbon nanocapsules. J Nanomater 2012:843516. https://doi.org/10.1155/2012/843516

    Article  CAS  Google Scholar 

  51. Atkins P, Overton T, Rourke J, Weller M, Armstrong F (2009) Shriver and atkins’ inorganic chemistry, 5th edn. OUP Oxford, New York

    Google Scholar 

  52. DiDonato M, Sarkar B (1997) Copper transport and its alterations in Menkes and Wilson diseases. Biochimica et Biophysica Acta (BBA) - Mol Basis Dis 1360:3–16

    Article  CAS  Google Scholar 

  53. Tapiero H, Townsend DM, Tew KD (2003) Trace elements in human physiology and pathology. Copp Biomed Pharmacother 57:386–398. https://doi.org/10.1016/S0753-3322(03)00012-X

    Article  CAS  Google Scholar 

  54. Hiroko K, Chie F, Wattanaporn B (2012) Inherited copper transport disorders: biochemical mechanisms, diagnosis, and treatment. Curr Drug Metab 13:237–250. https://doi.org/10.2174/138920012799320455

    Article  Google Scholar 

  55. Bandmann O, Weiss KH, Kaler SG (2015) Wilson’s disease and other neurological copper disorders. Lancet Neurol 14:103–113. https://doi.org/10.1016/S1474-4422(14)70190-5

    Article  CAS  Google Scholar 

  56. Liu J, Simms M, Song S, King RS, Cobb GP (2018) Physiological effects of copper oxide nanoparticles and arsenic on the growth and life cycle of rice (Oryza sativa japonica ‘Koshihikari’). Environ Sci Technol 52:13728–13737. https://doi.org/10.1021/acs.est.8b03731

    Article  CAS  Google Scholar 

  57. Chan Y-H, Jin Y, Wu C, Chiu DT (2011) Copper(ii) and iron(ii) ion sensing with semiconducting polymer dots. Chem Commun 47(10):2820–2822. https://doi.org/10.1039/C0CC04929H

    Article  CAS  Google Scholar 

  58. Gao J, Yin J, Tao Z, Liu Y, Lin X, Deng J, Wang S (2018) An ultrasensitive fluorescence sensor with simple operation for Cu2+ specific detection in drinking water. ACS Omega 3:3045–3050. https://doi.org/10.1021/acsomega.7b01497

    Article  CAS  Google Scholar 

  59. Xu X, Daniel WL, Wei W, Mirkin CA (2010) Colorimetric Cu2+ detection using DNA-modified gold-nanoparticle aggregates as probes and click chemistry. Small 6(5):623–626. https://doi.org/10.1002/smll.200901691

    Article  CAS  Google Scholar 

  60. Liu X, Zong C, Lu L (2012) Fluorescent silver nanoclusters for user-friendly detection of Cu2+ on a paper platform. Analyst 137(10):2406–2414. https://doi.org/10.1039/C2AN35051C

    Article  CAS  Google Scholar 

  61. Mehta VN, Kumar MA, Kailasa SK (2013) Colorimetric detection of copper in water samples using dopamine dithiocarbamate-functionalized Au nanoparticles. Ind Eng Chem Res 52(12):4414–4420. https://doi.org/10.1021/ie302651f

    Article  CAS  Google Scholar 

  62. Huang GG, Yang J (2003) Selective detection of copper ions in aqueous solution based on an evanescent wave infrared absorption spectroscopic method. Anal Chem 75(10):2262–2269. https://doi.org/10.1021/ac0264372

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by the NSF grant CHE 1709160, NSF Coorperative Agreement Award OIA-1946202 and Applied Research to Address the State’s Critical Needs Initiative program of UND A&S College Image Analysis Core Facility is supported in part by NIH grant 1P20GM113123 and P20GM103442. We also acknowledge the contribution of Miss. Shuyi He for helping to edit the manuscript.

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Liu, X., Han, J., Hou, X. et al. One-pot synthesis of graphene quantum dots using humic acid and its application for copper (II) ion detection. J Mater Sci 56, 4991–5005 (2021). https://doi.org/10.1007/s10853-020-05583-6

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