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Research Article

High brightness NIR-II nanofluorophores based on fused-ring acceptor molecules

Xingfu Zhu1,§Chunchen Liu1,§Zhubin Hu2,3,§Haile Liu4,§Jiang Wang1Yang Wang1Xinyuan Wang1Rui Ma1Xiaodong Zhang4( )Haitao Sun2,3( )Yongye Liang1( )
Department of Materials Science and Engineering, Shenzhen Key Laboratory of Printed Organic Electronic, Southern University of Science and Technology, Shenzhen 518055, China
State Key Laboratory of Precision Spectroscopy, East China Normal University, Shanghai 200062, China
Collaborative Innovation Center of Extreme Optics, Shanxi University, Taiyuan 030006, China
Department of Physics and Tianjin Key Laboratory of Low Dimensional Materials Physics and Preparing Technology, School of Science, Tianjin University, Tianjin 300350, China

§ Xingfu Zhu, Chunchen Liu, Zhubin Hu, and Haile Li contributed equally to this work.

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Abstract

It is challenging to develop molecular fluorophores in the second near-infrared (NIR-II) window with long wavelength emission and high brightness, which can improve the performance of biological imaging. Herein, we report a molecular engineering approach to afford NIR-II fluorophores with these merits based on fused-ring acceptor (FRA) molecules. Dioctyl 3,4-propylenedioxy thiophene (PDOT-C8) is utilized as the bridging donor to replace 3-ethylhexyloxy thiophene (3-EHOT), leading to more than 20 times enhancement of brightness. The nanofluorophores (NFs) based on the optimized CPTIC-4F molecule exhibit an emission peak of 1,110 nm with a fluorescence quantum yield (QY) of 0.39% (QY of IR-26 is 0.050% in dichloroethane as reference) and peak absorption coefficient of 14.5 × 104 M-1·cm-1 in aqueous solutions, which are significantly higher than those of 3-EHOT based COTIC-4F NFs. It is found that PDOT-C8 can weaken intermolecular aggregation, enhance protection of molecular backbone from water, and decrease backbone distortion, beneficial for the high brightness. Compared with indocyanine green with same injection dose, CPTIC-4F NFs show 10 times higher signal-to-background ratio for whole body vessels imaging at 1,300 nm long pass filters.

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References

[1]
Hong, G. S.; Antaris, A. L.; Dai, H. J. Near-infrared fluorophores for biomedical imaging. Nat. Biomed. Eng. 2017, 1, 0010.
[2]
Bashkatov, A. N.; Genina, E. A.; Kochubey, V. I.; Tuchin, V. V. Optical properties of human skin, subcutaneous and mucous tissues in the wavelength range from 400 to 2,000 nm. J. Phys. D: Appl. Phys. 2005, 38, 2543-2555.
[3]
Li, J. C.; Pu, K. Y. Development of organic semiconducting materials for deep-tissue optical imaging, phototherapy and photoactivation. Chem. Soc. Rev. 2019, 48, 38-71.
[4]
Jiang, Y.; Pu, K. Molecular fluorescence and photoacoustic imaging in the second near-infrared optical window using organic contrast agents. Adv. Biosyst. 2018, 2, 1700262.
[5]
Smith, A. M.; Mancini, M. C.; Nie, S. M. Second window for in vivo imaging. Nat. Nanotechnol. 2009, 4, 710-711.
[6]
Miao, Q. Q.; Pu, K. Y. Organic semiconducting agents for deep-tissue molecular imaging: Second near-infrared fluorescence, self-luminescence, and photoacoustics. Adv. Mater. 2018, 30, 1801778.
[7]
Ding, F.; Zhan, Y. B.; Lu, X. J.; Sun Y. Recent advances in near-infrared II fluorophores for multifunctional biomedical imaging. Chem. Sci. 2018, 9, 4370-4380.
[8]
Kenry; Duan, Y. K.; Liu, B. Recent advances of optical imaging in the second near-infrared window. Adv. Mater. 2018, 30, 1802394.
[9]
Qi, J.; Sun, C. W.; Zebibula, A.; Zhang, H. Q.; Kwok, R. T. K.; Zhao, X. Y.; Xi, W.; Lam, J. W. Y.; Qian, J.; Tang, B. Z. Real-time and high-resolution bioimaging with bright aggregation-induced emission dots in short-wave infrared region. Adv. Mater. 2018, 30, 1706856.
[10]
Sheng, Z. H.; Guo, B.; Hu, D. H.; Xu, S. D.; Wu, W. B.; Liew, W. H.; Yao, K.; Jiang, J. J.; Liu, C. B.; Zheng, H. R. et al. Bright aggregation-induced-emission dots for targeted synergetic NIR-II fluorescence and NIR-I photoacoustic imaging of orthotopic brain tumors. Adv. Mater. 2018, 30, 1800766.
[11]
Zhang, X. D.; Wang, H. S.; Antaris, A. L.; Li, L. L.; Diao, S.; Ma, R.; Nguyen, A.; Hong, G. S.; Ma, Z. R.; Wang, J. et al. Traumatic brain injury imaging in the second near-infrared window with a molecular fluorophore. Adv. Mater. 2016, 28, 6872-6879.
[12]
Yang, Q. L.; Ma, Z. R.; Wang, H. S.; Zhou, B.; Zhu, S. J.; Zhong, Y. T.; Wang, J. Y.; Wan, H.; Antaris, A.; Ma, R. et al. Rational design of molecular fluorophores for biological imaging in the NIR-II window. Adv. Mater. 2017, 29, 1605497.
[13]
Yang, Q. L.; Hu, Z. B.; Zhu, S. J.; Ma, R.; Ma, H. L.; Ma, Z. R.; Wan, H.; Zhu, T.; Jiang, Z. Y.; Liu, W. Q. et al. Donor engineering for NIR-II molecular fluorophores with enhanced fluorescent performance. J. Am. Chem. Soc. 2018, 140, 1715-1724.
[14]
Wan, H.; Yue, J. Y.; Zhu, S. J.; Uno, T.; Zhang, X. D.; Yang, Q. L.; Yu, K.; Hong, G. S.; Wang, J. Y.; Li, L. L. et al. A bright organic NIR-II nanofluorophore for three-dimensional imaging into biological tissues. Nat. Commun. 2018, 9, 1171.
[15]
Wan, H.; Ma, H. L.; Zhu, S. J.; Wang, F. F.; Tian, Y.; Ma, R.; Yang, Q. L.; Hu, Z. B.; Zhu, T.; Wang, W. Z. et al. Developing a bright NIR-II fluorophore with fast renal excretion and its application in molecular imaging of immune checkpoint PD-L1. Adv. Funct. Mater. 2018, 28, 1804956.
[16]
Tian, R.; Ma, H. L.; Yang, Q. L.; Wan, H.; Zhu, S. J.; Chandra, S.; Sun, H. T.; Kiesewetter, D. O.; Niu, G.; Liang, Y. Y. et al. Rational design of a super-contrast NIR-II fluorophore affords high-performance NIR-II molecular imaging guided microsurgery. Chem. Sci. 2019, 10, 326-332.
[17]
Antaris, A. L.; Chen, H.; Cheng, K.; Sun, Y.; Hong, G. S.; Qu, C. R.; Diao, S.; Deng, Z. X.; Hu, X. M.; Zhang, B. et al. A small-molecule dye for NIR-II imaging. Nat. Mater. 2016, 15, 235-242.
[18]
Huang, J. G.; Xie, C.; Zhang, X. D.; Jiang, Y. Y.; Li, J. C.; Fan, Q. L.; Pu, K. Y. Renal-clearable molecular semiconductor for second near-infrared fluorescence imaging of kidney dysfunction. Angew. Chem., Int. Ed. 2019, 58, 15120-15127.
[19]
Li, B. H.; Lu, L. F.; Zhao, M. Y.; Lei, Z. H.; Zhang, F. An efficient 1,064 nm NIR-II excitation fluorescent molecular dye for deep-tissue high-resolution dynamic bioimaging. Angew. Chem., Int. Ed. 2018, 57, 7483-7487.
[20]
Wang, S. F.; Fan, Y.; Li, D. D.; Sun, C. X.; Lei, Z. H.; Lu, L. F.; Wang, T.; Zhang, F. Anti-quenching NIR-II molecular fluorophores for in vivo high-contrast imaging and pH sensing. Nat. Commun. 2019, 10, 1058.
[21]
Sun, C. X.; Li, B. H.; Zhao, M. Y.; Wang, S. F.; Lei, Z. H.; Lu, L. F.; Zhang, H. X.; Feng, L. S.; Dou, C. R.; Yin, D. R. et al. J-aggregates of cyanine dye for NIR-II in vivo dynamic vascular imaging beyond 1500 nm. J. Am. Chem. Soc. 2019, 141, 19221-19225.
[22]
Lin, Y. Z.; Wang, J. Y.; Zhang, Z. G.; Bai, H. T.; Li, Y. F.; Zhu, D. B.; Zhan, X. W. An electron acceptor challenging fullerenes for efficient polymer solar cells. Adv. Mater. 2015, 27, 1170-1174.
[23]
Lin, Y. Z.; Zhang, Z. G.; Bai, H. T.; Wang, J. Y.; Yao, Y. H.; Li, Y. F.; Zhu, D. B.; Zhan, X. W. High-performance fullerene-free polymer solar cells with 6.31% efficiency. Energy Environ. Sci. 2015, 8, 610-616.
[24]
Li, T. F.; Dai, S. X.; Ke, Z. F.; Yang, L. X.; Wang, J. Y.; Yan, C. Q.; Ma, W.; Zhan, X. W. Fused tris(thienothiophene)-based electron acceptor with strong near-infrared absorption for high-performance as-cast solar cells. Adv. Mater. 2018, 30, 1705969.
[25]
Yan, C. Q.; Barlow, S.; Wang, Z. H.; Yan, H.; Jen, A. K. Y.; Marder, S. R.; Zhan, X. W. Non-fullerene acceptors for organic solar cells. Nat. Rev. Mater. 2018, 3, 18003.
[26]
Li, X. Z.; Liu, L.; Li, S. L.; Wan, Y. P.; Chen, J. X.; Tian, S.; Huang, Z. M.; Xiao, Y. F.; Cui, X.; Xiang, C. Y. et al. Biodegradable π-conjugated oligomer nanoparticles with high photothermal conversion efficiency for cancer theranostics. ACS Nano 2019, 13, 12901-12911.
[27]
Wang, Q.; Xu, J. Z.; Geng, R. Y.; Cai, J.; Li, J.; Xie, C.; Tang, W. H.; Shen, Q. M.; Huang, W.; Fan, Q. L. High performance one-for-all phototheranostics: NIR-II fluorescence imaging guided mitochondria-targeting phototherapy with a single-dose injection and 808 nm laser irradiation. Biomaterials 2020, 231, 119671.
[28]
Lee, J.; Ko, S. J.; Seifrid, M.; Lee, H.; Luginbuhl, B. R.; Karki, A.; Ford, M.; Rosenthal, K.; Cho, K.; Nguyen, T. Q. et al. Bandgap narrowing in non-fullerene acceptors: Single atom substitution leads to high optoelectronic response beyond 1,000 nm. Adv. Energy Mater. 2018, 8, 1801212.
[29]
Lee, J.; Ko, S. J.; Lee, H.; Huang, J. F.; Zhu, Z. Y.; Seifrid, M.; Vollbrecht, J.; Brus, V. V.; Karki, A.; Wang, H. B. et al. Side-chain engineering of nonfullerene acceptors for near-infrared organic photodetectors and photovoltaics. ACS Energy Lett. 2019, 4, 1401-1409.
[30]
Tao, Z. M.; Hong, G. S.; Shinji, C.; Chen, C. X.; Diao, S.; Antaris, A. L.; Zhang, B.; Zou, Y. P.; Dai, H. J. Biological imaging using nanoparticles of small organic molecules with fluorescence emission at wavelengths longer than 1,000 nm. Angew. Chem., Int. Ed. 2013, 52, 13002-13006.
[31]
Cosco, E. D.; Caram, J. R.; Bruns, O. T.; Franke, D.; Day, R. A.; Farr, E. P.; Bawendi, M. G.; Sletten, E. M. Flavylium polymethine fluorophores for near- and shortwave infrared imaging. Angew. Chem., Int. Ed. 2017, 56, 13126-13129.
[32]
Prosposito, P.; Casalboni, M.; De Matteis, F.; Glasbeek, M.; Quatela, A.; van Veldhoven, E.; Zhang, H. Femtosecond dynamics of IR molecules in hybrid materials. J. Lumin. 2001, 94-95, 641-644.
[33]
Prosposito, P.; Casalboni, M.; De Matteis, F.; Quatela, A., Glasbeek, M.; van Veldhoven, E.; Zhang, H. IR-luminescent molecules in hybrid materials. J. Sol-Gel Sci. Technol. 2003, 26, 909-913.
[34]
Birks, J. B. Photophysics of Aromatic Molecules; Wiley: London, 1970.
[35]
Runge, E.; Gross, E. K. U. Density-functional theory for time-dependent systems. Phys. Rev. Lett. 1984, 52, 997-1000.
[36]
Hohenberg, P.; Kohn, W. Inhomogeneous electron gas. Phys. Rev. 1964, 136, B864-B871.
[37]
Sun, H. T.; Autschbach, J. Electronic energy gaps for π-conjugated oligomers and polymers calculated with density functional theory. J. Chem. Theory Comput. 2014, 10, 1035-1047.
[38]
Alder, B. J.; Wainwright, T. E. Studies in molecular dynamics. I. General method. J. Chem. Phys. 1959, 31, 459-466.
[39]
Zhang, Z.; Fang, X. F.; Liu, Z. H.; Liu, H. C.; Chen, D. D.; He, S. Q.; Zheng, J.; Yang, B.; Qin, W. P.; Zhang, X. J. et al. Semiconducting polymer dots with dual-enhanced NIR-IIa fluorescence for through-skull mouse-brain imaging. Angew. Chem., Int. Ed. 2020, 59, 3691-3698.
Nano Research
Pages 2570-2575
Cite this article:
Zhu X, Liu C, Hu Z, et al. High brightness NIR-II nanofluorophores based on fused-ring acceptor molecules. Nano Research, 2020, 13(9): 2570-2575. https://doi.org/10.1007/s12274-020-2901-y
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Received: 13 March 2020
Revised: 20 May 2020
Accepted: 23 May 2020
Published: 22 June 2020
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020
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