Hydroxylated graphene quantum dots as fluorescent probes for sensitive detection of metal ions

Abstract

Highly sensitive methods are important for monitoring the concentration of metal ions in industrial wastewater. Here, we developed a new probe for the determination of metal ions by fluorescence quenching. The probe consists of hydroxylated graphene quantum dots (H-GQDs), prepared from GQDs by electrochemical method followed by surface hydroxylation. It is a non-reactive indicator with high sensitivity and detection limits of 0.01 μM for Cu²⁺, 0.005 μM for Al³⁺, 0.04 μM for Fe³⁺, and 0.02 μM for Cr³⁺. In addition, the low biotoxicity and excellent solubility of H-GQDs make them promising for application in wastewater metal ion detection.

Keywords

graphene quantum dots / surface hydroxylation / metal ions detection / fluorescent probes

References

[1] Li B, He ZS, Zhou HX, Zhang H, Li W, Cheng TY, Liu GH. Reaction based colorimetric and fuorescence probes for selective detection of hydrazine. Dyes Pigm., 2017, 146, 300

[2] Yao J, Yang M, Duan YX. Chemistry, biology, and medicine of fluorescent nanomaterials and related systems: newinsights into biosensing, bioimaging, genomics, dagnostics, and therapy. Chem. Rev., 2014, 114, 6130

[3] Aron AT, Reeves AG, Chang CJ. Activity-based sensing fluorescent probes for iron in biological systems. Curr. Opin. Chem. Biol, 2018, 43, 113

[4] Cho DJ, Sessler JL. Modern reaction-based indicator systems. Chem. Soc. Rev., 2009, 38, 1647

[5] Roy P, Chen PC, Periasamy AP, Chen YN, Chang HT. Photoluminescent carbon nanodots: Synthesis, physicochemical properties and analytical applications. Mater. Today, 2014, 18, 447

[6] Wen J, Xu YQ, Li HJ, Lu AP, Sun SG. Recent applications of carbon nanomaterials in fluorescence biosensing and bioimaging. Chem. Commun., 2015, 51, 11346

[7] Song YB, Zhu SJ, Yang B. Bioimaging based on fluorescent carbon dots. RSC Adv, 2014, 4, 27184

[8] Lin LP, Song XH, Chen YY, Rong MC, Wang YR, Zhao L, Zhao TT, Chen X. Europium-decorated graphene quantum dots as a fluorescent probe for label-free, rapid and sensitive detection of Cu²⁺ and l-cysteine. Anal. Chim. Acta, 2015, 891, 261

[9] Li Y, Liu XQ, Li QY, Ge J, Liu H, Li S, Wang LF, Wang J, Ma N. Post-oxidation treated graphene quantum dots as a fluorescent probe for sensitive detection of copper ions. Chem. Phys. Lett., 2016, 664, 127

[10] Fu XC, Jin JZ, Wu J, Jin JC, Xie CG. A novel “turn-on” fluorescence sensor for high selectively detecting Al (III) in aqueous solution based on simple electrochemical synthesized carbon dots. Anal Methods, 2017, 9, 3941

[11] Qu KG, Wang JS, Ren JS, Qu XG. Carbon dots prepared by hydrothermal treatment of dopamine as an effective fluorescent sensing platform for the label-free detection of iron(III) ions and dopamine. Chem. Eur. J., 2013, 19, 7243

[12] Wang BJ, Zhuo SJ, Chen LY, Zhang YJ. Fluorescent graphene quantum dot nanoprobes for the sensitive and selective detection of mercury ions. Spectrochim. Acta Part A, 2014, 131, 384

[13] Sharma S, Umar A, Mehta SK, Kansal SK. Fluorescent spongy carbon nanoglobules derived from pineapple juice: A potential sensing probe for specific and selective detection of chromium (VI) ions. Ceram. Int, 2017, 43, 7011

[14] Wang FX, Gu ZY, Lei W, Wang WJ, Xia XF, Hao QL. Graphene quantum dots as a fluorescent sensing platform for highly efficient detection of copper(II) ions. Sens. Actuators B, 2014, 190, 516

[15] Niu XF, Zhong YB, Chen R, Wang F, Liu YJ, Luo D. A “turn-on” fluorescence sensor for Pb²⁺ detection based on graphene quantum dots and gold nanoparticles. Sens. Actuators B, 2018, 255, 1577

[16] Zhou SH, Xu HB, Gan W, Yuan QH. Graphene quantum dots: Recent progress in preparation and fluorescence sensing applications. RSC Adv., 2016, 6, 110775

[17] Zhu SJ, Zhang JH, Qiao CY, Tang SJ, Li YF, Yuan WJ, Li B, Tian L, Liu F, Hu R, Gao HN, Wei HT, Zhang H, Sun HC, Yang B. Strongly green-photolu-minescent graphene quantum dots for bioimaging applications. Chem. Commun., 2011, 47, 6858

[18] Feng YQ, Zhao JP, Yan XB, Tang FL, Xue QJ. Enhancement in the fluorescence of graphene quantum dots by hydrazine hydrate reduction. Carbon, 2014, 66, 334

[19] Qian ZS, Shan XY, Chai LJ, Chen JR, Feng H. A fluorescent nanosensor based on graphene quantum dots-aptamer probe and graphene oxide platform for detection of lead (II) ion. Biosens. Bioelectron, 2015, 68, 225

[20] Li Y, Liu XQ, Wang J, Liu H, Li S, Hou YB, Wan W, Xue WD, Ma N, Zhang JZ. Chemical nature of redox-controlled photoluminescence of graphene quantum dots by post-synthesis treatment. J. Phys. Chem. C, 2016, 120, 26004

[21] Li Y, Liu H, Liu XQ, Li S, Wang LF, Ma N, Qiu DL. Free-radical-assisted rapid synthesis of graphene quantum dots and their oxidizability studies. Langmur, 2016, 32, 8641

[22] Luo PH, Qiu Y, Guan XF, Jiang LQ. Regulation of photoluminescence properties of graphene quantum dots via hydrothermal treatment. Phys. Chem. Chem. Phys., 2014, 16, 19011

[23] Zhu SJ, Zhang JH, Tang SJ, Qiao CY, Wang L, Wang HY, Liu X, Li B, Li YF, Yu WL, Wang XF, Sun HC, Yang B. Surface chemistry routes to modulate the photoluminescence of graphene quantum dots: From fluorescence mechanism to up-conversion bioimaging applications. Adv. Funct. Mater., 2012, 22, 4732

[24] Li LL, Wu GH, Yang GH, Peng J, Zhao JW, Zhu JJ. Focusing on luminescent graphene quantum dots: Current status and future perspectives. Nanoscale, 2013, 10, 4015

[25] Hu SL, Trinchi A, Atkin P, Cole I. Tunable photolu-minescence across the entire visible spectrum from carbon dots excited by white light. Angew. Chem. Int. Ed, 2015, 54, 2970

[26] Fan TJ, Zeng WJ, Tang W, Yuan CQ, Tong SZ, Cai KY, Liu YD, Huang W, Min Y, Epstein AJ. Controllable size-selective method to prepare graphene quantum dots from graphene oxide. Nanoscale Res. Lett, 2015, 10, 55

[27] Lakowicz JR. Principles of Fluorescence Spectroscopy, 2006, 3rd, New York, Springer Science+Business Media, LLC

[28] Zhang CQ, Yan Y, Pan QH, Sun LB, He HM, Liu YL, Liang ZQ, Li JY. A microporous lanthanum metal-organic framework as a bi-functional chemosensor for the detection of picric acid and Fe³⁺ ions. Dalton Trans., 2015, 44, 13340

[29] Zhou XH, Li L, Li HH, Li A, Yang T, Huang W. A flexible Eu(III)-based metal-organic framework: Turn-offluminescent sensor for the detection of Fe(III) and picric acid. Dalton Trans., 2013, 42, 12403

[30] Dong XQ, Li CL, Li J, Huang WT, Wang J, Liao RB. Application of a system dynamics approach for assessment of the impact of regulations on cleaner production in the electroplating industry in China. J. Cleaner Prod, 2012, 20, 72

[31] Shi L, Shi JS, Shi Y. Discussion on the emission standard of pollutants for electroplating. Electroplat. Finish., 2009, 28, 44

[32] Shen C, Ge SY, Pang YY, Xi FN, Liu JY, Dong XP, Chen P. Facile and scalable preparation of highly luminescent N,S co-doped graphene quantum dots and their application for parallel detection of multiple metal ions. J. Mater. Chem. B, 2017, 5, 6593

[33] Liu XF, Gao W, Zhou XM, Ma YY. Pristine graphene quantum dots for detection of copper ions. J. Mater. Res., 2014, 29, 1401

[34] Dujols V, Ford F, Czarnik AW. A long-wavelength fluorescent chemodosimeter selective for Cu(II) ion in water. J. Am. Chem. Soc, 1997, 119, 7386

[35] an L F, Qin JC, Li TR, Wang BD, Yang ZY. A novel rhodamine chromone-based “Off-On” chemo sensor for the differential detection of Al(III) and Zn(II) in aqueous solutions. Sens. Actuators B, 2014, 203, 550

[36] Wang D, Wang L, Dong XY, Shi Z, Jin J. Chemically tailoring graphene oxides into fluorescent nanosheets for Fe³⁺ ion detection. Carbon, 2012, 50, 2147

[37] Ju J, Chen W. Synthesis of highly fluorescent nitrogen-doped graphene quantum dots for sensitive, label-free detection of Fe (III) in aqueous media. Biosens. Bioelectron., 2014, 58, 219

[38] Yi C, Tian WW, Song B, Zheng YP, Qi ZJ, Qi Q, Sun YM. A new turn-offfluorescent chemosensor for iron (III) based on new diphenylfluorenes with phosphonic acid. J. Lumin., 2013, 141, 15

[39] Liu LQ, Li YF, Zhan L, Liu Y, Huang CZ. One-step synthesis of fluorescent hydroxyls-coated carbon dots with hydrothermal reaction and its application to optical sensing of metal ions. Sci. China Chem, 2011, 54, 1342

[40] Chen YF, Kao CL, Huang PC, Hsu CY, Kuei CH. Facile synthesis of multi-responsive functional graphene quantum dots for sensing metal cations. RSC Adv., 2016, 6, 103006

[41] Xin JW, Mao LJ, Chen SG, Wu AG. Colorimetric detection of Cr³⁺ using tripolyphosphate modified gold nanoparticles in aqueous solutions. Anal. Methods, 2012, 4, 1259

[42] Huang H, Weng YH, Zheng LH, Yao BX, Weng W, Lin XC. Nitrogen-doped carbon quantum dots as fluorescent probe for “off-on” detection of mercury ions, L-cysteine and iodide ions. J. Colloid Interface Sci, 2017, 506, 373