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Fatima, Anam 
ORCID: https://orcid.org/0000-0003-2388-4390, Ashworth, Eleanor K., Bressan, Giovanni ORCID: https://orcid.org/0000-0001-7801-8495, B. Page, Philip C., Bull, James N. ORCID: https://orcid.org/0000-0003-0953-1716 and Meech, Stephen R. ORCID: https://orcid.org/0000-0001-5561-2782
(2024)
Substituent effects on the photophysics of the kaede chromophore.
Physical Chemistry Chemical Physics, 26 (46).
pp. 29048-29059.
ISSN 1463-9076
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Abstract
Kaede is the prototype of the optical highlighter proteins, which are an important subclass of the fluorescent proteins that can be permanently switched from green to red emitting forms by UV irradiation. This transformation has important applications in bioimaging. Optimising brightness, i.e. enhancing fluorescence characteristics, in these proteins is an important objective. At room temperature, the excited state dynamics of the red form of the kaede chromophore are dominated by a broad distribution of conformers with distinct excited state kinetics. Here, we investigate substituent effects on the photophysics of this form of the kaede chromophore. While an electron withdrawing substituent (nitro) red shifts the electronic spectra, the modified chromophores showed no significant solvatochromism. The lack of solvatochromism suggests small changes in permanent dipole moment between ground and excited electronic states, which is consistent with quantum chemical calculations. Ultrafast fluorescence and transient absorption spectroscopy reveal correlations between radiative and nonradiative decay rates of different conformers in the chromophores. The most significant effect of the substituents is to modify the distribution of conformers. The results are discussed in the context of enhancing brightness of optical highlighter proteins.
| Item Type: | Article |
|---|---|
| Additional Information: | Data availability statement; Additional data and coordinates from calculations are available in supplementary information. Funding information: Financial support to SRM (EP/X011410/1, EP/V00817X/1, EP/J009148/1) and JNB (EP/W018691/1). EKA thanks UEA for the award of a studentship. |
| Faculty \ School: | Faculty of Science > School of Chemistry, Pharmacy and Pharmacology |
| UEA Research Groups: | Faculty of Science > Research Groups > Centre for Photonics and Quantum Science Faculty of Science > Research Groups > Chemistry of Light and Energy |
| Related URLs: | |
| Depositing User: | LivePure Connector |
| Date Deposited: | 08 Nov 2024 12:30 |
| Last Modified: | 02 Dec 2024 01:44 |
| URI: | https://ueaeprints.uea.ac.uk/id/eprint/97597 |
| DOI: | 10.1039/D4CP03272A |
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