中国物理B ›› 2023, Vol. 32 ›› Issue (5): 57801-057801.doi: 10.1088/1674-1056/ac80af

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Theoretical investigation on the fluorescent sensing mechanism for recognizing formaldehyde: TDDFT calculation and excited-state nonadiabatic dynamics

Yunfan Yang(杨云帆)1,3,†, Lujia Yang(杨璐佳)1, Fengcai Ma(马凤才)2, Yongqing Li(李永庆)2,‡, and Yue Qiu(邱岳)4   

  1. 1 Key Laboratory for Microstructural Material Physics of Hebei Province, School of Science, Yanshan University, Qinhuangdao 066004, China;
    2 Department of Physics, Liaoning University, Shenyang 110036, China;
    3 State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China;
    4 Grimwade Centre for Cultural Materials Conservation, School of Historical and Philosophical Studies, Faculty of Arts University of Melbourne, Parkville, VIC 3052, Australia
  • 收稿日期:2022-06-02 修回日期:2022-06-29 接受日期:2022-07-13 出版日期:2023-04-21 发布日期:2023-04-26
  • 通讯作者: Yunfan Yang, Yongqing Li E-mail:yangyunfan2626@163.com;yqli@lnu.edu.cn
  • 基金资助:
    Project supported by the National Natural Science Foundation of China (Grant No. 12104392); the Natural Science Foundation of Hebei Province, China (Grant No. B2021203017); the High-Level Innovative Talents Program of Shenyang City (Grant No. RC200565); and the Innovation Capability Improvement Project of Hebei Province, China (Grant No. 22567605H). The numerical calculations in this paper have been done on the supercomputing system in the High-Performance Computing Center of Yanshan University.

Theoretical investigation on the fluorescent sensing mechanism for recognizing formaldehyde: TDDFT calculation and excited-state nonadiabatic dynamics

Yunfan Yang(杨云帆)1,3,†, Lujia Yang(杨璐佳)1, Fengcai Ma(马凤才)2, Yongqing Li(李永庆)2,‡, and Yue Qiu(邱岳)4   

  1. 1 Key Laboratory for Microstructural Material Physics of Hebei Province, School of Science, Yanshan University, Qinhuangdao 066004, China;
    2 Department of Physics, Liaoning University, Shenyang 110036, China;
    3 State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China;
    4 Grimwade Centre for Cultural Materials Conservation, School of Historical and Philosophical Studies, Faculty of Arts University of Melbourne, Parkville, VIC 3052, Australia
  • Received:2022-06-02 Revised:2022-06-29 Accepted:2022-07-13 Online:2023-04-21 Published:2023-04-26
  • Contact: Yunfan Yang, Yongqing Li E-mail:yangyunfan2626@163.com;yqli@lnu.edu.cn
  • Supported by:
    Project supported by the National Natural Science Foundation of China (Grant No. 12104392); the Natural Science Foundation of Hebei Province, China (Grant No. B2021203017); the High-Level Innovative Talents Program of Shenyang City (Grant No. RC200565); and the Innovation Capability Improvement Project of Hebei Province, China (Grant No. 22567605H). The numerical calculations in this paper have been done on the supercomputing system in the High-Performance Computing Center of Yanshan University.

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摘要： Inspired by the activity-based sensing method, the hydrazine-modified naphthalene derivative (Naph1) was synthesized and used as a fluorescent probe to detect formaldehyde (FA) in living cells. Through the condensation reaction between the probe Naph1 and analyte FA, researchers observed a ～ 14 folds enhancement of fluorescent signal around 510 nm in an experiment, realizing the high selectivity and sensitivity detection of FA. However, a theoretical understanding of the sensing mechanism was not provided in the experimental work. Given this, the light-up fluorescent detecting mechanism was in-depth unveiled by performing the time-dependent density functional theory (TDDFT) and the complete active space self-consistent field (CASSCF) theoretical calculations on excited-state intramolecular proton transfer (ESIPT) and non-adiabatic excited-state dynamics simulation. The deactivation channel of S1/T2 intersystem crossing (ISC) was turned off to successfully recognize FA. Insight into the ESIPT-based fluorescent detecting mechanism indicated that ESIPT was essential to light-up fluorescent probes. This work would provide a new viewpoint to develop ESIPT-based fluorescent probes for detecting reactive carbon species in vivo or vitio.

关键词: proton transfer, twisting intramolecular charge transfer, intersystem crossing, fluorescent probe

Abstract: Inspired by the activity-based sensing method, the hydrazine-modified naphthalene derivative (Naph1) was synthesized and used as a fluorescent probe to detect formaldehyde (FA) in living cells. Through the condensation reaction between the probe Naph1 and analyte FA, researchers observed a ～ 14 folds enhancement of fluorescent signal around 510 nm in an experiment, realizing the high selectivity and sensitivity detection of FA. However, a theoretical understanding of the sensing mechanism was not provided in the experimental work. Given this, the light-up fluorescent detecting mechanism was in-depth unveiled by performing the time-dependent density functional theory (TDDFT) and the complete active space self-consistent field (CASSCF) theoretical calculations on excited-state intramolecular proton transfer (ESIPT) and non-adiabatic excited-state dynamics simulation. The deactivation channel of S1/T2 intersystem crossing (ISC) was turned off to successfully recognize FA. Insight into the ESIPT-based fluorescent detecting mechanism indicated that ESIPT was essential to light-up fluorescent probes. This work would provide a new viewpoint to develop ESIPT-based fluorescent probes for detecting reactive carbon species in vivo or vitio.

Key words: proton transfer, twisting intramolecular charge transfer, intersystem crossing, fluorescent probe

中图分类号:  (Excited states)

  • 78.47.da
33.15.Hp (Barrier heights (internal rotation, inversion, rotational isomerism, conformational dynamics)) 87.15.ht (Ultrafast dynamics; charge transfer) 33.20.-t (Molecular spectra)