Abstract
Carbon quantum dots (CQDs) are drawing tremendous attention due to their unique photoluminescence property and fascinating functions. Herein, we prepared novel CQDs functionalized with amino acids (AA-CQDs) by a one-pot hydrothermal method for selective detection of Al3+ ions and fluorescence imaging. The prepared AA-CQDs exhibit a novel triple-excitation and single-colour emission for fluorescent property. In addition, the AA-CQDs have a high absolute quantum yield (24.23%) and quantum lifetime (13.29 ns). Moreover, the AA-CQDs exhibit high selectivity and sensitivity for Al3+ by fluorescence enhancement. In pH 7.4 PBS solution, there was a good linear relation between the fluorescence intensity and the concentration of Al3+ in the range of 1–20 μmol L−1; the limit of detection (3σ) was only 0.32 μmol L−1. Furthermore, an AA-CQD probe was also utilized for detection of Al3+ in living cells based on excellent biocompatibility and endocytosis. Based on the concentration of Al3+ ions in cells and apoptosis data, there will be a quick reflect of apoptosis induced by aluminium ions via the fluorescence intensity of the AA-CQD probe. This work will set the stage for developing novel CQD-based biosensors in cell research.
Graphical abstract
![](http://media.springernature.com/lw685/springer-static/image/art%3A10.1007%2Fs00216-021-03348-x/MediaObjects/216_2021_3348_Figa_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00216-021-03348-x/MediaObjects/216_2021_3348_Fig1_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00216-021-03348-x/MediaObjects/216_2021_3348_Fig2_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00216-021-03348-x/MediaObjects/216_2021_3348_Fig3_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00216-021-03348-x/MediaObjects/216_2021_3348_Fig4_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00216-021-03348-x/MediaObjects/216_2021_3348_Fig5_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00216-021-03348-x/MediaObjects/216_2021_3348_Fig6_HTML.png)
Similar content being viewed by others
References
Han GM, Zhao J, Zhang RL, Tian XH, Liu ZJ, Wang AD, et al. Membrane-penetrating carbon quantum dots for imaging nucleic acid structures in live organisms. Angew Chem. 2019;5(21):7087–91.
Zheng XT, Ananthanarayanan A, Luo KQ, Chen P. Glowing graphene quantum dots and carbon dots: properties, syntheses, and biological applications. Small. 2015;11(14):1620–36.
Chen WF, Li DJ, Tian L, Xiang W, Wang TY, Hu WM, et al. Synthesis of graphene quantum dots from natural polymer starch for cell imaging. Green Chem. 2018;40(19):4438–42.
Lim SY, Shen W, Gao Z. Carbon quantum dots and their applications. Chem Soc Rev. 2015;44(1):362–81.
Jiji RD, Cooper GA, Booksh KS. Excitation-emission matrix fluorescence based determination of carbamate pesticides and polycyclic aromatic hydrocarbons. Anal Chim Acta. 1999;397:61–72.
Bortolato SA, Arancibia JA, Escandar GM. Non-trilinear chromatographic time retention−fluorescence emission data coupled to chemometric algorithms for the simultaneous determination of 10 polycyclic aromatic hydrocarbons in the presence of interferences. Anal Chem. 2009;81(19):8074–84.
Zhu ZJ, Zhai YL, Li ZH, Zhu PY, Mao S, Zhu CZ, et al. Red carbon dots: optical property regulations and applications. Mater Today. 2019;30:52–79.
Liang Q, Shi Y, Li Z, Yang XM. Easy synthesis of highly fluorescent carbon quantum dots from gelatin and their luminescent properties and applications. Carbon. 2013;60:421–8.
Liu J, Geng Y, Li D, Yang B. Deep red emissive carbonized polymer dots with unprecedented narrow full width at half maximum. Adv Mater. 2020;32(17):1906641.
Yan C, Hu X, Guan P, et al. Highly biocompatible graphene quantum dots: green synthesis, toxicity comparison and fluorescence imaging. J Mater Sci. 2020;55(3):1198–215.
Wang M, Yin H, Zhou Y. A novel photoelectrochemical biosensor for the sensitive detection of dual micrornas using molybdenum carbide nanotubes as nanocarriers and energy transfer between CQDs and AuNPs. Chem Eng J. 2019;369:351–7.
Liu T, Dong JX, Liu SG, Li N, Li NB. Carbon quantum dots prepared with polyethyleneimine as both reducing agent and stabilizer for synthesis of Ag/CQDs composite for Hg2+ ions detection. J Hazard Mater. 2017;322(Pt B):430–6.
Liu J, Chen P, Xia F, Liu Z, Zhou C. Sensitive electrochemiluminescence aptasensor for chlorpyrifos detection based on resonance energy transfer between MoS2/CdS nanospheres and Ag/CQDs. Sensors Actuators B Chem. 2020;315:128098.
Singha P, Vat BG, Jha SK, Neogy S. Green, water-dispersible photoluminescent on–off–on probe for selective detection of fluoride ions. ACS Appl Mater Interfaces. 2017;9(24):20536–44.
Fan Q, Li J, Zhu Y, Yang Z, Wang X. Functional carbon quantum dots towards highly sensitive graphene transistors for Cu2+ ion detection. ACS Appl Mater Interfaces. 2020;12(4):4797–803.
Yan C, Wang C, Hou T, Guan P, Wu H. Lasting tracking and rapid discrimination of live gram-positive bacteria by peptidoglycan-targeting carbon quantum dots. ACS Appl Mater Interfaces. 2021;13(1):1277–87.
Yue J, Li L, Cao L, Zan M, Dong WF. Two-step hydrothermal preparation of carbon dots for calcium ion detection. ACS Appl Mater Interfaces. 2019;11(47):44566–72.
Tripathi KM, Tran TS, Kim YJ. Green fluorescent onion-like carbon nanoparticles from flaxseed oil for visible light induced photocatalytic applications and label-free detection of Al(III) ions. ACS Sustain Chem Eng. 2017;5(5):3982–92.
Fang BY, Li C, Song YY. Nitrogen-doped graphene quantum dot for direct fluorescence detection of Al3+ in aqueous media and living cells. Biosens Bioelectron. 2017;100:41–8.
Cassella RJ, Magalhaes OIB, Couto MT, Lima ELS, Neves MAFS, Coutinho FMB. Synthesis and application of a functionalized resin for flow injection/FAAS copper determination in waters. Talanta. 2005;67(1):121–8.
Frankowski M, Zioła-Frankowska A, Siepak J. Speciation of aluminium fluoride complexes and Al3+ in soils from the vicinity of an aluminium smelter plant by hyphenated high performance ion chromatography flame atomic absorption spectrometry technique. Microchem J. 2010;95(2):366–72.
Park SH, Kwon N, Lee JH, Yoon J, Shin I. Synthetic ratiometric fluorescent probes for detection of ions. Chem Soc Rev. 2020;49(1):143–79.
Li H, Fan J, Peng X. Colourimetric and fluorescent probes for the optical detection of palladium ions. Chem Soc Rev. 2013;42(19):7943–62.
Prabhu AJ, et al. Pyrene-phenylglycinol linked reversible ratiometric fluorescent chemosensor for the detection of aluminium in nanomolar range and its bio-imaging. Anal Chim Acta. 2019;1090:114–24.
Chen P, et al. Thiol inhibition of Hg cold vapor generation in SnCl2/NaBH4 system: a homogeneous bioassay for H2O2/glucose and butyrylcholinesterase/pesticide sensing by atomic spectrometry. Anal Chim Acta. 2020;1111:8–15.
Liu D, Wang Z, Jiang X. Gold nanoparticles for the colorimetric and fluorescent detection of ions and small organic molecules. Nanoscale. 2011;3(4):1421–33.
Hassan M, Gomes VG, Dehghani A, Ardekani SM. Engineering carbon quantum dots for photomediated theranostics. Nano Res 2017;11(1):1–41.
Zhang R, Chen W. Nitrogen-doped carbon quantum dots: facile synthesis and application as a “turn-off” fluorescent probe for detection of Hg2+ ions. Biosens Bioelectron. 2014;55:83–90.
Shu P, Liu S. Dual-emission carbon dots for ratiometric detection of Fe3+ ions and acid phosphatase. Anal Chim Acta. 2020;1105:155–61.
Qi HJ, Teng M, Liu M, Liu SX, Li J, Yu HP, et al. Biomass-derived nitrogen-doped carbon quantum dots: highly selective fluorescent probe for detecting Fe3+ ions and tetracyclines. J Colloid Interface Sci. 2019;39:332–41.
Xie ZH, Sun XF, Jiao JM, Xin X. Ionic liquid-functionalized carbon quantum dots as fluorescent probes for sensitive and selective detection of iron ion and ascorbic acid. Colloids Surf A Physicochem Eng Asp. 2017;529:38–44.
Li HY, Xu Y, Zhao L, Ding J, Chen MY, Chen GR, et al. Synthesis of tiny carbon dots with high quantum yield using multi-walled carbon nanotubes as support for selective “turn-off-on” detection of rutin and Al3+. Carbon. 2019;143:391–401.
Xia C, Cao MM, Xia JF, Jiang DY, Zhou GH, Yu CY, et al. Preparation of tunable full-color emission carbon dots and their optical applications in ions detection and bio-imaging. J Am Ceram Soc. 2020;103(8):4507–16.
Yan FY, Jiang YX, Sun XD, Wei JF, Chen L, Zhang YY. Multicolor carbon dots with concentration-tunable fluorescence and solvent-affected aggregation states for white light-emitting diodes. Nano Res. 2020;13(1):52–60.
Emam HE, Ahmed HB. Antitumor/antiviral carbon quantum dots based on carrageenan and pullulan. Int J Biol Macromol. 2020;170:688–700.
Jiang K, Gao X, Feng X, et al. Carbon dots with dual-emissive, robust and aggregation-induced room temperature phosphorescence characteristics. Angew Chem Int Ed. 2019;59(3):1263–9.
Ge M, Huang X, Ni J, Han Y, et al. One-step synthesis of self-quenching-resistant biomass-based solid-state fluorescent carbon dots with high yield for white lighting emitting diodes. Dyes Pigments. 2021;185:108953.
Han Z, Ni Y, Ren J, et al. Highly efficient and ultra-narrow bandwidth orange emissive carbon dots for microcavity lasers. Nanoscale. 2019;11(24):11577–83.
Wang Y, Ge G, Gao J, Li Z, et al. Multicenter-emitting carbon dots: color tunable fluorescence and dynamics monitoring oxidative stress in vivo. Chem Mater. 2020;32(19):8146–57.
Bai LH, Yan HX, Feng YB, Feng WX, Yuan LY. Multi-excitation and single color emission carbon dots doped with silicon and nitrogen: synthesis, emission mechanism, Fe3+ probe and cell imaging. Chem Eng J. 2019;373:963–72.
Ahmad S, Wan N, Ismail AF, Yusof N, Aziz F. Adsorptive removal of heavy metal ions using graphene-based nanomaterials: toxicity, roles of functional groups and mechanisms. Chemosphere. 2020;248:126008.
Jal PK, Patel S, Mishra BK. Chemical modification of silica surface by immobilization of functional groups for extractive concentration of metal ions. Talanta. 2004;62(5):1005–28.
Caicedo M, Jacobs JJ, Reddy A, James N. Hallab Analysis of metal ion-induced DNA damage, apoptosis, and necrosis in human (Jurkat) T-cells demonstrates Ni2+ and V3+ are more toxic than other metals: Al3+, Be2+, Co2+, Cr3+, Cu2+, Fe3+, Mo5+, Nb5+, Zr2+. J Biomed Mater Res Part A. 2008;86(4):905–13.
Qu SH, Sun FY, Qiao ZH, Li JM, Shang L. In situ investigation on the protein corona formation of quantum dots by using fluorescence resonance energy transfer. Small. 2020;16(21):1907633.
Yan C, Zhang N, Guan P, et al. Drug-based magnetic imprinted nanoparticles: enhanced lysozyme amyloid fibrils cleansing and anti-amyloid fibrils toxicity. Int J Biol Macromol. 2020;153:723–35.
Acknowledgements
We thank the Analytical and Testing Centre of Northwestern Polytechnical University for equipment supporting.
Funding
This work was supported financially by the National Natural Science Foundation of China (Grant No. 51433008, 81571786, 31771087), Shaanxi Innovation Capability Support Plan (2020TD-041), Shaanxi Key Research & Development Program Foundation (2020GY-285) and Shaanxi Natural Science Foundation (2021JM-238).
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
ESM 1
(PDF 1.71 mb)
Rights and permissions
About this article
Cite this article
Yan, C., Guo, L., Shao, X. et al. Amino acid–functionalized carbon quantum dots for selective detection of Al3+ ions and fluorescence imaging in living cells. Anal Bioanal Chem 413, 3965–3974 (2021). https://doi.org/10.1007/s00216-021-03348-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00216-021-03348-x