A photoelectron imaging study of the deprotonated GFP chromophore anion and RNA fluorescent tags. Issue 35 (2nd September 2021)

• Record Type: Journal Article
• Authors: Woodhouse, Joanne L.; Henley, Alice; Lewin, Ross; Ward, John M.; Hailes, Helen C.; Bochenkova, Anastasia V.; Fielding, Helen H.
• Is Part Of: Physical chemistry chemical physics. Volume 23:Issue 35(2021)
• Page Start: 19911
• Page End: 19922
• Publication Date: 2021-09-02
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d1cp01901e
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Green fluorescent protein (GFP), together with its family of variants, is the most widely used fluorescent protein for in vivo imaging. An investigation of the influence of fluorine and methoxy substituents on the electronic structure of the GFP chromophore. Abstract : Green fluorescent protein (GFP), together with its family of variants, is the most widely used fluorescent protein for in vivo imaging. Numerous spectroscopic studies of the isolated GFP chromophore have been aimed at understanding the electronic properties of GFP. Here, we build on earlier work [A. V. Bochenkova, C. Mooney, M. A. Parkes, J. Woodhouse, L. Zhang, R. Lewin, J. M. Ward, H. Hailes, L. H. Andersen and H. H. Fielding, Chem. Sci., 2017, 8, 3154] investigating the impact of fluorine and methoxy substituents that have been employed to tune the electronic structure of the GFP chromophore for use as fluorescent RNA tags. We present photoelectron spectra following photoexcitation over a broad range of wavelengths (364–230 nm) together with photoelectron angular distributions following photoexcitation at 364 nm, which are interpreted with the aid of quantum chemistry calculations. The results support the earlier high-level quantum chemistry calculations that predicted how fluorine and methoxy substituents tune the electronic structure and we find evidence to suggest that the methoxy substituents enhance internal conversion, most likely from the 2ππ* state which has predominantly Feshbach resonance character, to the 1ππ* state.