Green fluorescent protein (GFP) has enabled a myriad of bioimaging advances due to its photophysical and photochemical properties. To deepen the mechanistic understanding of such light-induced processes, novel derivatives of GFP chromophore p-HBDI were engineered by fluorination or bromination of the phenolic moiety into superphotoacids, which efficiently undergo excited-state proton transfer (ESPT) in aqueous solution within the short lifetime of the excited state, as opposed to p-HBDI where efficient ESPT is not observed. In addition, we tuned the excited-state lifetime from picoseconds to nanoseconds by conformational locking of the p-HBDI backbone, essentially transforming the nonfluorescent chromophores into highly fluorescent ones. The unlocked superphotoacids undergo a barrierless ESPT without much solvent activity, whereas the locked counterparts exhibit two distinct solvent-involved ESPT pathways. Comparative analysis of femtosecond transient absorption spectra of these unlocked and locked superphotoacids reveals that the ESPT rates adopt an “inverted” kinetic behavior as the thermodynamic driving force increases upon locking the backbone. Further experimental and theoretical investigations are expected to shed more light on the interplay between the modified electronic structure (mainly by dihalogenation) and nuclear motions (by conformational locking) of the functionalized GFP derivatives (e.g., fluorescence on and off).
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14 January 2020
Rapid Communication|
January 13 2020
Ultrafast excited-state proton transfer dynamics in dihalogenated non-fluorescent and fluorescent GFP chromophores
Special Collection:
Ultrafast molecular sciences by femtosecond photons and electrons
Cheng Chen
;
Cheng Chen
a)
1
Department of Chemistry, Oregon State University
, 153 Gilbert Hall, Corvallis, Oregon 97331, USA
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Liangdong Zhu
;
Liangdong Zhu
a)
1
Department of Chemistry, Oregon State University
, 153 Gilbert Hall, Corvallis, Oregon 97331, USA
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Sean A. Boulanger;
Sean A. Boulanger
1
Department of Chemistry, Oregon State University
, 153 Gilbert Hall, Corvallis, Oregon 97331, USA
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Nadezhda S. Baleeva;
Nadezhda S. Baleeva
2
Institute of Bioorganic Chemistry, Russian Academy of Sciences
, Miklukho-Maklaya 16/10, Moscow 117997, Russia
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Ivan N. Myasnyanko;
Ivan N. Myasnyanko
2
Institute of Bioorganic Chemistry, Russian Academy of Sciences
, Miklukho-Maklaya 16/10, Moscow 117997, Russia
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Mikhail S. Baranov;
Mikhail S. Baranov
2
Institute of Bioorganic Chemistry, Russian Academy of Sciences
, Miklukho-Maklaya 16/10, Moscow 117997, Russia
3
Pirogov Russian National Research Medical University
, Ostrovitianov 1, Moscow 117997, Russia
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Chong Fang
Chong Fang
b)
1
Department of Chemistry, Oregon State University
, 153 Gilbert Hall, Corvallis, Oregon 97331, USA
b)Author to whom correspondence should be addressed: [email protected]
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Cheng Chen
1,a)
Liangdong Zhu
1,a)
Sean A. Boulanger
1
Nadezhda S. Baleeva
2
Ivan N. Myasnyanko
2
Mikhail S. Baranov
2,3
Chong Fang
1,b)
1
Department of Chemistry, Oregon State University
, 153 Gilbert Hall, Corvallis, Oregon 97331, USA
2
Institute of Bioorganic Chemistry, Russian Academy of Sciences
, Miklukho-Maklaya 16/10, Moscow 117997, Russia
3
Pirogov Russian National Research Medical University
, Ostrovitianov 1, Moscow 117997, Russia
a)
Contributions: C. Chen and L. Zhu contributed equally to this work.
b)Author to whom correspondence should be addressed: [email protected]
Note: This paper is part of the JCP Special Topic on Ultrafast Molecular Sciences by Femtosecond Photons and Electrons.
J. Chem. Phys. 152, 021101 (2020)
Article history
Received:
November 14 2019
Accepted:
December 24 2019
Citation
Cheng Chen, Liangdong Zhu, Sean A. Boulanger, Nadezhda S. Baleeva, Ivan N. Myasnyanko, Mikhail S. Baranov, Chong Fang; Ultrafast excited-state proton transfer dynamics in dihalogenated non-fluorescent and fluorescent GFP chromophores. J. Chem. Phys. 14 January 2020; 152 (2): 021101. https://doi.org/10.1063/1.5138666
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