Enhancing Brightness and Photostability of Organic Small Molecular Fluorescent Dyes Through Inhibiting Twisted Intramolecular Charge Transfer (TICT)※

doi:10.6023/A21120578

Acta Chimica Sinica ›› 2022, Vol. 80 ›› Issue (4): 553-562.DOI: 10.6023/A21120578 Previous Articles Next Articles

Special Issue: 中国科学院青年创新促进会合辑

Review

基于抑制扭转的分子内电荷转移(TICT)提升有机小分子荧光染料亮度及光稳定性^※

许宁^a^,^b, 乔庆龙^a^,^*(), 刘晓刚^c, 徐兆超^a^,^b^,^*()

a 中国科学院大连化学物理研究所辽宁大连 116023
b 大连理工大学张大煜学院辽宁大连 116024
c 新加坡科技设计大学新加坡 487372

投稿日期:2021-12-23 发布日期:2022-04-28
通讯作者: 乔庆龙, 徐兆超

作者简介:

许宁, 博士研究生, 2018年7月毕业于山东理工大学化学化工学院, 获理学硕士学位. 目前就读于大连理工大学张大煜(化学)学院, 主要从事新型荧光团的开发以及荧光成像工作.

乔庆龙, 大连化学物理研究所副研究员. 2017年获得大连理工大学博士学位, 2018年加入大连化学物理研究所徐兆超教授课题组, 2020年任副研究员, 主要研究方向为新型荧光染料开发、超分辨动态成像和蛋白质荧光探针.

徐兆超, 大连化学物理研究所研究员, 博士生导师. 2006年毕业于大连理工大学, 师从钱旭红教授. 随后, 进入梨花女子大学的Juyoung Yoon教授课题组, 担任博士后研究员. 2008年10月起在剑桥大学David R. Spring教授课题组担任Herchel Smith Research Fellow. 2011年至今在中国科学院大连化学物理研究所任课题组组长. 主要研究方向为新型的荧光团设计和发光构效关系研究、蛋白质标记和传感、荧光探针、超分辨率荧光成像.

^※ 庆祝中国科学院青年创新促进会十年华诞.

基金资助:
国家自然科学基金(22078314); 国家自然科学基金(21878286); 国家自然科学基金(21908216); 大连化学物理研究所(DICPI202142); 大连化学物理研究所(DICPI201938); 大连化学物理研究所(DICPZZBS201805); 新加坡教育部(MOE-MOET2EP10120-0007); 新加坡科技设计大学(SUTD-ZJU(SUTD-ZJU (VP) 201905)

Enhancing Brightness and Photostability of Organic Small Molecular Fluorescent Dyes Through Inhibiting Twisted Intramolecular Charge Transfer (TICT)^※

Ning Xu^a^,^b, Qinglong Qiao^a(), Xiaogang Liu^c, Zhaochao Xu^a^,^b()

a Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China
b Zhang Dayu School of Chemistry, Dalian University of Technology, Dalian 116024, China
c Singapore University of Technology and Design, Singapore 487372, Singapore

Received:2021-12-23 Published:2022-04-28
Contact: Qinglong Qiao, Zhaochao Xu
About author:
^※ Dedicated to the 10th anniversary of the Youth Innovation Promotion Association, CAS.
Supported by:
National Natural Science Foundation of China(22078314); National Natural Science Foundation of China(21878286); National Natural Science Foundation of China(21908216); Dalian Institute of Chemical Physics(DICPI202142); Dalian Institute of Chemical Physics(DICPI201938); Dalian Institute of Chemical Physics(DICPZZBS201805); The authors thank the support from the Ministry of Education, Singapore(MOE-MOET2EP10120-0007); Singapore University of Technology and Design(SUTD-ZJU (VP) 201905)

During the past 170 years, organic small molecular fluorescent dyes had been widely applied in fluorescence labeling, fluorescence probes and bioimaging. And their structures and performances continually evolved with development of synthetic method and application. However, the emerging super-resolution imaging put forward higher requirements at brightness, stability and switching performance of organic small molecular fluorescent dyes, which also offers new opportunity for developing novel dyes at the same time. So, chemists presently pay more attentions on brightness and photostability. Twisted intramolecular charge transfer (TICT), the major nonradiative decay channel in organic small molecular fluorescent dyes, seriously decrease brightness and photostability. Therefore, inhibiting TICT has became the crucial strategy to develop organic small molecular fluorescent dyes towards super-resolution imaging. This review will firstly demonstrate mechanism and development of TICT and emphatically introduce the progress in improving organic small molecular fluorescent dyes based on inhibiting TICT.

Key words: super-resolution imaging, organic small molecular fluorescent dyes, twisted intramolecular charge transfer, brightness, photostability

Cite this article

Ning Xu, Qinglong Qiao, Xiaogang Liu, Zhaochao Xu. Enhancing Brightness and Photostability of Organic Small Molecular Fluorescent Dyes Through Inhibiting Twisted Intramolecular Charge Transfer (TICT)^※[J]. Acta Chimica Sinica, 2022, 80(4): 553-562.

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Fig. & Tab. 15

Figure 1. (a) Hypothesized excited-state equilibrium (the TICT model); (b) illustration of energy potential surfaces for excited-state molecular twisting in a donor-acceptor (D-A) type fluorophore[32-33]; (c) fluorescence excitation and emission spectra of DMAPB in aqueous solutions containing 1% (V/V) MeCN[35]

Figure 2. The illustration of the TICT mechanism from (a) experimental view and (b) the corresponding parameters[26]

Figure 3. Amino cyclization strategy in various fluorophores inhibits TICT and improves quantum yield

Figure 4. (a) Chemical structures and (b) spectroscopic properties of 9 and 10 measured in water. (c) The UV-Vis absorption spectra of 9 and 10 as a function of laser irradiation time[31]

Figure 5. Chemical structures and spectroscopic properties of 11~16 measured in water

Figure 6. (a) Schematic illustration of steric hindrance between the donor and naphthalimide fragments. (b) Schematic illustration of various donor conformations and optimized geometries of 17~19. (c) Chemical structures and (d) spectroscopic properties of 17~19 measured in EtOH[44]

Figure 7. (a) Chemical structures and (b) spectroscopic properties of SA2 and MY measured in PBS

Figure 8. (a) Chemical structures and (b) spectroscopic properties of 20 and 21 measured in water

Figure 9. (a) Chemical structures and (b) spectroscopic properties of 11, 22~26 measured in water

Figure 10. (a) Chemical structures and (b) spectroscopic properties of 27~31 measured in PBS

Figure 11. (a) Chemical structures and (b) spectroscopic properties of 32 and 33 measured in water

Figure 12. (a) Chemical structures, (b) spectroscopic properties measured in EtOH of 19 and 34 and (c) electron density difference during excitation calculated for 19 and 34[51]

Figure 13. (a) Possible approaches to mitigate the dye photobluing unrelated to TICT suppression, (b) chemical structures and (c) time-resolved absorption spectra of 35[52]

Figure 14. (a) Chemical structures of 11, 36~38 and (b) spectroscopic properties of them measured in HEPES buffer. (c) Sequential absorption spectra of 11 and 36 during photobleaching using 560 nm (1.02 W/cm2)[58]

Figure 15. (a) Chemical structures of 32, 39 and 40 and (b) spectroscopic properties of them measured in PBS solution. (c) Relative S1 energy as a function of the N-TICT rotation angle (θ) for them calculated at the CAM-B3LYP/cLR-SMD level in water solution[62]

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基于抑制扭转的分子内电荷转移(TICT)提升有机小分子荧光染料亮度及光稳定性^※

Enhancing Brightness and Photostability of Organic Small Molecular Fluorescent Dyes Through Inhibiting Twisted Intramolecular Charge Transfer (TICT)^※

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基于抑制扭转的分子内电荷转移(TICT)提升有机小分子荧光染料亮度及光稳定性※

Enhancing Brightness and Photostability of Organic Small Molecular Fluorescent Dyes Through Inhibiting Twisted Intramolecular Charge Transfer (TICT)※

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References 62

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基于抑制扭转的分子内电荷转移(TICT)提升有机小分子荧光染料亮度及光稳定性^※

Enhancing Brightness and Photostability of Organic Small Molecular Fluorescent Dyes Through Inhibiting Twisted Intramolecular Charge Transfer (TICT)^※