Deep Eutectic Solvent-assisted Synthesis of Nitrogen-doped Carbon Quantum Dots for Cell Imaging

Abstract

Carbon quantum dots(CQDs) are widely used in fluorescence imaging due to their negligible toxicity, low-cost and excellent fluorescence properties. The fluorescence properties of CQDs are greatly affected by the synthesis method, passivation agent and reaction media. In this study, the nitrogen-doped CQDs(N-CQDs) were synthesized by a facile microwave-assisted method with citric acid(CA) as a carbon source and deep eutectic solvents as a N-dopant as well as the reaction solvent. After detailed characterizations, the as-prepared N-CQDs exhibited near spherical morphology with an average size of (2.64±0.55) nm. Besides, the abundant hydrophilic functional groups including hydroxyl, carboxyl, amine and quaternary ammonium were present on the surface of the N-CQDs. The N-CQDs displayed the excitation-dependent fluorescence feature under the excitation wavelength of 350–480 nm. Moreover, the N-CQDs could be efficiently uptaken by RAW264.7 cells and emitted bright green light. Meanwhile, the resultant N-CQDs showed the low cytotoxicity in living cells, suggesting the great potential in bio-imaging applications.

Keywords

N-Dopant carbon quantum dot / Microwave / Deep eutectic solvent / Green light emission / Cell imaging

References

[1] Liu Q, Guo B, Rao Z, Zhang B, Gong J R. Nano Lett., 2013, 13(6): 2436.

[2] Huang S, Chen P, Xu C. Talanta, 2017, 165: 161.

[3] Yang S T, Cao L, Luo P G, Lu F, Wang X, Wang H, Meziani M J, Liu Y, Qi G, Sun Y P. J. Am. Chem. Soc., 2009, 131(32): 11308.

[4] Clapp A R, Pons T, Medintz I L, Delehanty J B, Melinger J S, Tiefenbrunn T, Dawson P E, Fisher B R, O’Rourke B, Mattoussi H. Adv. Mater., 2007, 19(15): 1921.

[5] Liu R, Wu D, Liu S, Koynov K, Knoll W, Li Q. Angew. Chem. Int. Ed., 2009, 48(25): 4598.

[6] Geys J, Nemmar A, Verbeken E, Smolders E, Ratoi M, Hoylaerts M F, Nemery B, Hoet P H. Environ. Health Perspect., 2008, 116(12): 1607.

[7] Xue B, Yang Y, Sun Y, Fan J, Li X, Zhang Z. Int. J. Biol. Macromol., 2019, 122: 954.

[8] Song W, Duan W, Liu Y, Ye Z, Chen Y, Chen H, Qi S, Wu J, Liu D, Xiao L, Ren C, Chen X. Anal. Chem., 2017, 89(24): 13626.

[9] Wei L, Ma Y H, Shi X Y, Wang Y X, Su X, Yu C Y, Xiang S L, Xiao L H, Chen B. J. Mater. Chem. B., 2017, 5(18): 3383.

[10] Gao X H, Du C, Zhuang Z H, Chen W. J. Mater. Chem. C, 201, 4(29): 6927.

[11] Edison T N, Atchudan R, Sethuraman M G, Shim J J, Lee Y R. J. Photochem. Photobiol. B: Biol., 201, 161: 154.

[12] Gao M X, Liu C F, Wu Z L, Zeng Q L, Yang X X, Wu W B, Li Y F, Huang C Z. Chem. Commun., 2013, 49(73): 8015.

[13] Zhu H, Wang X, Li Y, Wang Z, Yang F, Yang X. Chem. Commun., 2009, 34: 5118.

[14] Fang Y, Guo S, Li D, Zhu C, Ren W, Dong S, Wang E. ACS Nano, 2012, 6(1): 400.

[15] Liu H, Yang J, Li Z, Xiao L, Aryee A A, Sun Y, Yang R, Meng H, Qu L, Lin Y, Zhang X. Anal. Chem., 2019, 91(14): 9259.

[16] Zhao L, Baccile N, Gross S, Zhang Y J, Wei W, Sun Y H, Anto-nietti M, Titirici M M. Carbon, 2010, 48(13): 3778.

[17] Jaiswal A, Ghsoh S S, Chattopadhyay A. Langmuir, 2012, 28(44): 15687.

[18] Castro H P, Souza V S, Scholten J D, Dias J H, Fernandes J A, Rodembusch F S, Dos R R, Dupont J, Teixeira S R, Correia R R. Chemistry, 201, 22(1): 138.

[19] Çalhan S D, Alaş M Ö, Aşık M, Kaya F N D, Genç R. J. Mater. Sci., 2018, 53(22): 15362.

[20] Plechkova N V, Seddon K R. Chem. Soc. Rev., 2008, 37(1): 123.

[21] Abbott A P, Boothby D, Capper G, Davies D L, Rasheed R K. J. Am. Chem. Soc., 2004, 126(29): 9142.

[22] Avalos M, Babiano R, Cintas P, Jimenez J L, Palacios J C. Angew. Chem. Int. Ed., 200, 45(24): 3904.

[23] Wang N, Zheng A Q, Liu X, Chen J J, Yang T, Chen M L, Wang J H. ACS Appl Mater Interfaces, 2018, 10(9): 7901.

[24] Wei L, Lu B A, Sun M J, Tian N, Zhou Z Y, Xu B B, Zhao X S, Sun S G. Nano Research, 201, 9(11): 3547.

[25] Shahbaz K, Mjalli F S, Hashim M A, AlNashef I M. Energy Fuels, 2011, 25(6): 2671.

[26] Ke Y T, Garg B, Ling Y C. RSC. Adv., 2014, 4(102): 58329.

[27] Feryforgues S. J. Chem. Educ., 2014, 76(9): 1260.

[28] Liu Y, Xiao N, Gong N, Wang H, Shi X, Gu W, Ye L. Carbon, 2014, 68: 258.

[29] Liu J, Li D, Zhang K, Yang M, Sun H, Yang B. Small, 2018, 14(15): e1703919.

[30] Ding H, Yu S B, Wei J S, Xiong H M. ACS Nano, 201, 10(1): 484.

[31] Yuan F, Wang Z, Li X, Li Y, Tan Z, Fan L, Yang S. Adv. Mater., 2017, 29(3): 1604436.

[32] Atchudan R, Edison T N J I, Perumal S, Selvam N C S, Lee Y R. J, Photoch. Photobio. A, 2019, 372: 99.

[33] Atchudan R, Edison T, Lee Y R. J. Colloid Interface Sci., 201, 482: 8.

[34] Zhu S, Meng Q, Wang L, Zhang J, Song Y, Jin H, Zhang K, Sun H, Wang H, Yang B. Angew. Chem. Int. Ed., 2013, 52(14): 3953.

[35] Fan Y, Guo X, Zhang Y, Lv Y, Zhao J, Liu X. ACS Appl. Mater. Interfaces., 201, 8(46): 31863.

[36] Yang M, Li B Y, Zhong K L, Lu Y. J. Mater. Sci., 2018, 53(4): 2424.

[37] Li K, Li P, Cai J, Xiao S, Yang H, Li A. Chemosphere, 201, 154: 310.

[38] Vallan L, Urriolabeitia E P, Ruiperez F, Matxain J M, Can-ton-Vitoria R, Tagmatarchis N, Benito A M, Maser W K. J. Am. Chem. Soc., 2018, 140(40): 12862.

[39] Qu D, Zheng M, Li J, Xie Z G, Sun Z C. Light: Sci. Appl., 2015, 4: e364.

[40] Verma N C, Rao C, Nandi C K. J. Phys. Chem. C, 2018, 122(8): 4704.

[41] Lee S D, Kim B M, Kim D W, Kim M I, Roshan K R, Kim M K, Won Y S, Park D W. Appl. Catal. A: Gen., 2014, 486: 69.

[42] Wang L, Zhu S J, Wang H Y, Qu S N, Zhang Y L, Zhang J H, Chen Q D, Xu H L, Han W, Yang B, Sun H B. ACS Nano, 2014, 8(3): 2541.

[43] Liu C, Zhang P, Zhai X, Tian F, Li W, Yang J, Liu Y, Wang H, Wang W, Liu W. Biomaterials, 2012, 33(13): 3604.

[44] Demchenko A P, Dekaliuk M O. Methods. Appl. Fluores., 2013, 1(4): 042001.

[45] Shi Y P, Pan Y, Zhong J, Yang J, Zheng J H, Cheng J L, Song R, Yi C Q. Carbon, 2015, 93: 742.

[46] Pan Y, Yang J, Fang Y N, Zheng J H, Song R, Yi C Q. J. Mater. Chem. B., 2017, 5(1): 92.