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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 Wang1, Yang Wang1, Xinyuan Wang1, Rui Ma1, Xiaodong 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.

Keywords

nanofluorophoresfused-ring acceptorpropylenedioxy thiophenehigh brightnesssecond near-infrared (NIR-II) biological imaging

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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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[5]
Smith, A. M.; Mancini, M. C.; Nie, S. M. Second window for in vivo imaging. Nat. Nanotechnol. 2009, 4, 710-711.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[8]
Kenry; Duan, Y. K.; Liu, B. Recent advances of optical imaging in the second near-infrared window. Adv. Mater. 2018, 30, 1802394.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Google Scholar
[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.
Google Scholar
[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.
Google Scholar
[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.
Google Scholar
[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.
Google Scholar
[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.
Google Scholar
[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.
Google Scholar
[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.
Google Scholar
[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.
Google Scholar
[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.
Google Scholar
[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.
Google Scholar
[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.
Google Scholar
[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.
Google Scholar
[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.
Google Scholar
[36]
Hohenberg, P.; Kohn, W. Inhomogeneous electron gas. Phys. Rev. 1964, 136, B864-B871.
Google Scholar
[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.
Google Scholar
[38]
Alder, B. J.; Wainwright, T. E. Studies in molecular dynamics. I. General method. J. Chem. Phys. 1959, 31, 459-466.
Google Scholar
[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.
Google Scholar
Nano Research
Volume 13 Issue 9,
September 2020
Pages 2570-2575
DOI: 10.1007/s12274-020-2901-y
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
Topics:
FluorophoresInfrared devices

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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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