Abstract
In this paper, intrinsic dual-emission fluorescent carbon dots (CDs) doped with N and S atoms have been firstly fabricated. The characterization results show that CDs are successfully synthesized with two separate fluorescence emissions at 468 nm and 628 nm, respectively. The strong and selective interaction of Cr (VI) ions with CDs lead to obvious fluorescence decrease of CDs at 468 nm, which is caused by a mixed quenching mechanism. At the same time, the fluorescence at 628 nm increase. Interestingly, the CDs solution show obvious color change under the daylight and UV light, so visualization detection of Cr (VI) can be realized in water samples. Based on the data of the emission intensity ratios of F468/F628, Cr (VI) can be detected from 3.8 to 38.9 μM combined with the linear correlation coefficient of 0.998, and the lowest detection concentration is 47.2 nM. The platform is satisfactorily applied to the detection of Cr (VI) ions in water samples. In addition, the CDs could be applied as fluorescent probes for cell imaging with dual fluorescent emission.
Graphical abstract
References
Sheng LY, Huangfu BH, Xu QH, Tian WL, Li ZJ, Meng A, et al. A highly selective and sensitive fluorescent probe for detecting Cr(VI) and cell imaging based on nitrogen-doped graphene quantum dots. J Alloy Compd. 2020;820. https://doi.org/10.1016/j.jallcom.2019.153191.
Yahyazadeh E, Shemirani F. Arginine-derived carbon nanoparticles for determination of Cr(VI) in water samples. Luminescence. 2020;35(5):694–701. https://doi.org/10.1002/bio.3774.
Zhang D, Jia B, Li M, Guo J, Wang T, Cao C, et al. A ratiometric fluorescent probe for sensitive and selective detection of chromium (VI) in aqueous solutions. Microchem J. 2020;159. https://doi.org/10.1016/j.microc.2020.105337.
Jigyasa, Kumar D, Arora P, Singh H, Rajput JK. Polyhydroquinoline nanoaggregates: a dual fluorescent probe for detection of 2,4,6-trinitrophenol and chromium (VI). Spectrochim Acta A Mol Biomol Spectrosc. 2020;230:118087. https://doi.org/10.1016/j.saa.2020.118087.
Huang S, Yang E, Yao J, Chu X, Liu Y, Xiao Q. Nitrogen, phosphorus and sulfur tri-doped carbon dots are specific and sensitive fluorescent probes for determination of chromium(VI) in water samples and in living cells. Mikrochim Acta. 2019;186(12):851. https://doi.org/10.1007/s00604-019-3941-4.
Powell MJ, Boomer DW. Determination of chromium species in environmental samples using high-pressure liquid chromatography direct injection nebulization and inductively coupled plasma mass spectrometry. Anal Chem. 1995;67:2474–8. https://doi.org/10.1021/ac00110a023.
Song OY, Islam MA, Son JH, Jeong JY, Kim HE, Yeon LS, et al. Elemental composition of pork meat from conventional and animal welfare farms by inductively coupled plasma-optical emission spectrometry (ICP-OES) and ICP-mass spectrometry (ICP-MS) and their authentication via multivariate chemometric analysis. Meat Sci. 2021;172: 108344. https://doi.org/10.1016/j.meatsci.2020.108344.
Silva AS, Brandao GC, Matos GD, Ferreira SLC. Direct determination of chromium in infant formulas employing high-resolution continuum source electrothermal atomic absorption spectrometry and solid sample analysis. Talanta. 2015;144:39–43. https://doi.org/10.1016/j.talanta.2015.05.046.
Li M, He R, Wang S, Feng C, Wu H, Mei H. Visible light driven photoelectrochemical sensor for chromium(VI) by using BiOI microspheres decorated with metallic bismuth. Mikrochim Acta. 2019;186(6):345. https://doi.org/10.1007/s00604-019-3463-0.
Assi N, Aberoomand Azar P, Saber Tehrani M, Husain SW, Darwish M, Pourmand S. Selective solid-phase extraction using 1,5-diphenylcarbazide-modified magnetic nanoparticles for speciation of Cr(VI) and Cr(III) in aqueous solutions. Int J Environ Sci Technol. 2018;16(8):4739–48. https://doi.org/10.1007/s13762-018-1868-7.
Tai D, Liu C, Liu J. Facile synthesis of fluorescent carbon dots from shrimp shells and using the carbon dots to detect chromium(VI). Spectrosc Lett. 2019;52(3–4):194–9. https://doi.org/10.1080/00387010.2019.1607879.
De Acha N, Elosua C, Corres JM, Arregui FJ. Fluorescent sensors for the detection of heavy metal ions in aqueous media. Sensors. 2019;19(3):599–633. https://doi.org/10.3390/s19030599.
Faraz M, Abbasi A, Naqvi FK, Khare N, Prasad R, Barman I, et al. Polyindole/cadmium sulphide nanocomposite based turn-on, multi-ion fluorescence sensor for detection of Cr3+, Fe3+ and Sn2+ ions. Sensor Actuat B: Chem. 2018;269:195–202. https://doi.org/10.1016/j.snb.2018.04.110.
Burratti L, Ciotta E, De Matteis F, Prosposito P. Metal nanostructures for environmental pollutant detection based on fluorescence. Nanomaterials. 2021;11(2):276. https://doi.org/10.3390/nano11020276.
Luo XL, Han Y, Chen XM, Tang WZ, Yue TL, Li ZH. Carbon dots derived fluorescent nanosensors as versatile tools for food quality and safety assessment: a review. Trends Food Sci Technol. 2020;95:149–61. https://doi.org/10.1016/j.tifs.2019.11.017.
Rao H, Liu W, He K, Zhao S, Lu Z, Zhang S, et al. Smartphone-based fluorescence detection of Al3+ and H2O based on the use of dual-emission biomass carbon dots. ACS Sustain Chem Eng. 2020;8(23):8857–67. https://doi.org/10.1021/acssuschemeng.0c03354.
Luo Q, Huang X, Luo Y, Yuan H, Ren T, Li X, et al. Fluorescent chitosan-based hydrogel incorporating titanate and cellulose nanofibers modified with carbon dots for adsorption and detection of Cr(VI). Chem Eng J. 2021;407. https://doi.org/10.1016/j.cej.2020.127050.
Wu L, Guo Q-S, Liu Y-Q, Sun Q-J. Fluorescence resonance energy transfer-based ratiometric fluorescent probe for detection of Zn2+ using a dual-emission silica-coated quantum dots mixture. Anal Chem. 2015;87(10):5318–23. https://doi.org/10.1021/acs.analchem.5b00514.
Yao C, Liu Q, Zhao N, Liu J-M, Fang G, Wang S. Ratiometric determination of Cr(VI) based on a dual-emission fluorescent nanoprobe using carbon quantum dots and a smartphone app. Microchim Acta. 2021;188(3):89. https://doi.org/10.1007/s00604-021-04747-8.
Cheng D, Pan Y, Wang L, Zeng Z, Yuan L, Zhang X, et al. Selective visualization of the endogenous peroxynitrite in an inflamed mouse model by a mitochondria-targetable two-photon ratiometric fluorescent probe. J Am Chem Soc. 2017;139(1):285–92. https://doi.org/10.1021/jacs.6b10508.
Tan Q, An X, Pan S, Liu H, Hu X. Hydrogen peroxide assisted synthesis of sulfur quantum dots for the detection of chromium (VI) and ascorbic acid. Spectrochim Acta A Mol Biomol Spectrosc. 2021;247:119122. https://doi.org/10.1016/j.saa.2020.119122.
Shojaeifard Z, Hemmateenejad B, Shamsipur M. Efficient on–off ratiometric fluorescence probe for cyanide ion based on perturbation of the interaction between gold nanoclusters and a copper(II)-phthalocyanine complex. ACS Appl Mater Inter. 2016;8(24):15177–86. https://doi.org/10.1021/acsami.6b01566.
Huang X, Song J, Yung BC, Huang X, Xiong Y, Chen X. Ratiometric optical nanoprobes enable accurate molecular detection and imaging. Chem Soc Rev. 2018;47(8):2873–920. https://doi.org/10.1039/C7CS00612H.
Wang H, Yang L, Chu S, Liu B, Zhang Q, Zou L, et al. Semiquantitative visual detection of lead ions with a smartphone via a colorimetric paper-based analytical device. Anal Chem. 2019;91(14):9292–9. https://doi.org/10.1021/acs.analchem.9b02297.
Babaee E, Barati A, Gholivand MB, Taherpour AA, Zolfaghar N, Shamsipur M. Determination of Hg(2+) and Cu(2+) ions by dual-emissive Ag/Au nanocluster/carbon dots nanohybrids: switching the selectivity by pH adjustment. J Hazard Mater. 2019;367:437–46. https://doi.org/10.1016/j.jhazmat.2018.12.104.
Wang Y, Zhang C, Chen X, Yang B, Yang L, Jiang C, et al. Ratiometric fluorescent paper sensor utilizing hybrid carbon dots-quantum dots for the visual determination of copper ions. Nanoscale. 2016;8(11):5977–84. https://doi.org/10.1039/c6nr00430j.
Song Y, Chen J, Hu D, Liu F, Li P, Li H, et al. Ratiometric fluorescent detection of biomakers for biological warfare agents with carbon dots chelated europium-based nanoscale coordination polymers. Sensor Actuat B: Chem. 2015;221:586–92. https://doi.org/10.1016/j.snb.2015.07.008.
Bai H, Tu Z, Liu Y, Tai Q, Guo Z, Liu S. Dual-emission carbon dots-stabilized copper nanoclusters for ratiometric and visual detection of Cr2O7(2-) ions and Cd(2+) ions. J Hazard Mater. 2020;386: 121654. https://doi.org/10.1016/j.jhazmat.2019.121654.
Wang Y, He J, Zheng M, Qin M, Wei W. Dual-emission of Eu based metal-organic frameworks hybrids with carbon dots for ratiometric fluorescent detection of Cr(VI). Talanta. 2019;191:519–25. https://doi.org/10.1016/j.talanta.2018.08.078.
Ma Y, Chen Y, Liu J, Han Y, Ma S, Chen X. Ratiometric fluorescent detection of chromium(VI) in real samples based on dual emissive carbon dots. Talanta. 2018;185:249–57. https://doi.org/10.1016/j.talanta.2018.03.081.
Cui Y, Liu R, Ye F, Zhao S. Single-excitation, dual-emission biomass quantum dots: preparation and application for ratiometric fluorescence imaging of coenzyme A in living cells. Nanoscale. 2019;11(19):9270–5. https://doi.org/10.1039/c9nr01809c.
Jiang X, Qin D, Mo G, Feng J, Zheng X, Deng B. Facile preparation of boron and nitrogen codoped green emission carbon quantum dots for detection of permanganate and captopril. Anal Chem. 2019;91(17):11455–60. https://doi.org/10.1021/acs.analchem.9b02938.
Liu J, Dong Y, Ma Y, Han Y, Ma S, Chen H, et al. One-step synthesis of red/green dual-emissive carbon dots for ratiometric sensitive ONOO(-) probing and cell imaging. Nanoscale. 2018;10(28):13589–98. https://doi.org/10.1039/c8nr04596h.
Zhang M, Su R, Zhong J, Fei L, Cai W, Guan Q, et al. Red/orange dual-emissive carbon dots for pH sensing and cell imaging. Nano Res. 2019;12(4):815–21. https://doi.org/10.1007/s12274-019-2293-z.
Hu Y, Yang Z, Lu X, Guo J, Cheng R, Zhu L, et al. Facile synthesis of red dual-emissive carbon dots for ratiometric fluorescence sensing and cellular imaging. Nanoscale. 2020;12(9):5494–500. https://doi.org/10.1039/d0nr00381f.
Shao K, Yang Y, Ye S, Gu D, Wang T, Teng Y, et al. Dual-colored carbon dots-based ratiometric fluorescent sensor for high-precision detection of alkaline phosphatase activity. Talanta. 2020;208: 120460. https://doi.org/10.1016/j.talanta.2019.120460.
Wu S, Li W, Sun Y, Zhang X, Zhuang J, Hu H, et al. Synthesis of dual-emissive carbon dots with a unique solvatochromism phenomenon. J Colloid Interface Sci. 2019;555:607–14. https://doi.org/10.1016/j.jcis.2019.07.089.
Wang Y, Lu L, Peng H, Xu J, Wang F, Qi R, et al. Multi-doped carbon dots with ratiometric pH sensing properties for monitoring enzyme catalytic reactions. Chem Commun (Camb). 2016;52(59):9247–50. https://doi.org/10.1039/c6cc02874h.
Yu L, Zhang L, Ren G, Li S, Zhu B, Chai F, et al. Multicolorful fluorescent-nanoprobe composed of Au nanocluster and carbon dots for colorimetric and fluorescent sensing Hg2+ and Cr6+. Sensor Actuators B Chem. 2018;262:678–86. https://doi.org/10.1016/j.snb.2018.01.192.
Xiang GQ, Ren Y, Zhang H, Fan HH, Jiang XM, He LJ, et al. Carbon dots based dual-emission silica nanoparticles as ratiometric fluorescent probe for chromium speciation analysis in water samples. Can J Chem. 2018;96(1):72–7. https://doi.org/10.1139/cjc-2017-0472.
Zhang HY, Wang Y, Xiao S, Wang H, Wang JH, Feng L. Rapid detection of Cr(VI) ions based on cobalt(II)-doped carbon dots. Biosens Bioelectron. 2017;87:46–52. https://doi.org/10.1016/j.bios.2016.08.010.
Li B, Ma H, Zhang B, Qian J, Cao T, Feng H, et al. Dually emitting carbon dots as fluorescent probes for ratiometric fluorescent sensing of pH values, mercury(II), chloride and Cr(VI) via different mechanisms. Mikrochim Acta. 2019;186(6):341. https://doi.org/10.1007/s00604-019-3437-2.
Zhang S, Jin L, Liu J, Wang Q, Jiao L. A label-free yellow-emissive carbon dot-based nanosensor for sensitive and selective ratiometric detection of chromium (VI) in environmental water samples. Mater Chem Phys. 2020;248. https://doi.org/10.1016/j.matchemphys.2020.122912.
Cao M, Li Y, Zhao Y, Shen C, Zhang H, Huang Y. A novel method for the preparation of solvent-free, microwave-assisted and nitrogen-doped carbon dots as fluorescent probes for chromium (VI) detection and bioimaging. Rsc Adv. 2019;9(15):8230–8. https://doi.org/10.1039/c9ra00290a.
Mutuyimana FP, Liu J, Nsanzamahoro S, Na M, Chen H, Chen X. Yellow-emissive carbon dots as a fluorescent probe for chromium (VI). Mikrochim Acta. 2019;186(3):163. https://doi.org/10.1007/s00604-019-3284-1.
Roshni V, Misra S, Santra MK, Ottoor D. One pot green synthesis of C-dots from groundnuts and its application as Cr (VI) sensor and in vitro bioimaging agent. J Photochem Photobiol A Chem. 2019;373:28–36. https://doi.org/10.1016/j.jphotochem.2018.12.028.
Liu S, Cui J, Huang J, Tian B, Jia F, Wang Z. Facile one-pot synthesis of highly fluorescent nitrogen-doped carbon dots by mild hydrothermal method and their applications in detection of Cr (VI) ions. Spectrochim Acta A Mol Biomol Spectrosc. 2019;206:65–71. https://doi.org/10.1016/j.saa.2018.07.082.
Ji X, Wang S, Luo Y, Yuan X, Wei Y, Zhang Q, et al. Green synthesis of weissella-derived fluorescence carbon dots for microbial staining, cell imaging and dual sensing of vitamin B12 and hexavalent chromium. Dyes Pigments. 2021;184. https://doi.org/10.1016/j.dyepig.2020.108818.
Sun XH, Yang SH, Guo MZ, Ma S, Zheng MD, He J. Reversible fluorescence probe based on N-doped carbon dots for the determination of mercury ion and glutathione in waters and living cells. Anal Sci. 2017;33:761–7. https://doi.org/10.2116/analsci.33.761.
Li G, Fu H, Chen X, Gong P, Chen G, Xia L, et al. Facile and sensitive fluorescence sensing of alkaline phosphatase activity with photoluminescent carbon dots based on inner filter effect. Anal Chem. 2016;88(5):2720–6. https://doi.org/10.1021/acs.analchem.5b04193.
Zhang Y, Fang X, Zhao H, Li Z. A highly sensitive and selective detection of Cr (VI) and ascorbic acid based on nitrogen-doped carbon dots. Talanta. 2018;181:318–25. https://doi.org/10.1016/j.talanta.2018.01.027.
Wang Y, Hu X, Li W, Huang X, Li Z, Zhang W, et al. Preparation of boron nitrogen co-doped carbon quantum dots for rapid detection of Cr(VI). Spectrochim Acta A Mol Biomol Spectrosc. 2020;243: 118807. https://doi.org/10.1016/j.saa.2020.118807.
Liu J, Chen Y, Wang L, Na M, Chen H, Chen X. Modification-free fabricating ratiometric nanoprobe based on dual-emissive carbon dots for nitrite determination in food samples. J Agric Food Chem. 2019;67(13):3826–36. https://doi.org/10.1021/acs.jafc.9b00024.
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This work was supported by the National Natural Science Foundation of China (No. 21874087) and Research Project Supported by Shanxi Scholarship Council of China (2021-011).
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Mei, X., Wang, D., Wang, S. et al. Synthesis of intrinsic dual-emission type N,S-doped carbon dots for ratiometric fluorescence detection of Cr (VI) and application in cellular imaging. Anal Bioanal Chem 414, 7253–7263 (2022). https://doi.org/10.1007/s00216-022-04277-z
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DOI: https://doi.org/10.1007/s00216-022-04277-z