A new twist in the photophysics of the GFP chromophore: a volume-conserving molecular torsion couple

Conyard, Jamie; Heisler, Ismael A.; Chan, Yohan; Page, Philip C. Bulman; Meech, Stephen R.; Blancafort, Lluı́s

doi:10.1039/c7sc04091a

Cited by 39 publications

(31 citation statements)

References 78 publications

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“…The calculations have been carried out in the gas phase, given that the solvent polarity effect on the dynamics is relatively small. This approach has proven reliable in a previous study of a similar excited‐state isomerization process . Key geometric parameters of the stationary points are provided in the Supporting Information.…”

Section: Resultsmentioning

confidence: 85%

“…This approachh as provenr eliable in ap revious study of as imilare xcited-state isomerization process. [49] Key geometric parameters of the sta-tionary points are providedi nt he Supporting Information. After excitation to S 2 at the FC geometry (ground-state minimum), compound 4 decayst ot he minimum of the pp*s tate, and then, without af urther barrier,t othat of the np*s tate.…”

Section: Resultsmentioning

confidence: 99%

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Picosecond Switchable Azo Dyes

García-Amorós

Maerz

Reig

et al. 2019

Chemistry A European J

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Azo dyes that combine electron-withdrawing thiazole/benzothiazole heterocyclesa nd electron-donating amino groups within the very same covalent skeleton exhibit relaxation times for their thermali somerization kinetics within milli-and microsecond timescales at room temperature. Notably,t he thermal back reactiono ft he corresponding benzothiazolium and thiazolium salts occurred much faster,w ithin the picosecond temporald omain. In fact, these new light-sensitive platforms are the first molecular azo derivativesc apable of reversibles witching between their trans and cis isomers in as ubnanosecond timescale under ambient conditions. In addition, theoretical calculations revealed very low activation energies for the isomerization process, in accordance with the fast subnanosecond kinetics that were observed experimentally.

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Section: Resultsmentioning

confidence: 85%

Section: Resultsmentioning

confidence: 99%

Picosecond Switchable Azo Dyes

García-Amorós

Maerz

Reig

et al. 2019

Chemistry A European J

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“…First, a large barrier to trans-cis isomerization via single bond rotation (ca 180 kJ mol −1 ) is calculated in the electronic ground state 26 and second evidence from electronic spectra is consistent with a neutral cis ground state being formed in picoseconds 14 . The photostationary state for the chromophore in solution (Figure 4) indeed showed only very slow trans to cis recovery in the ground state (several hours in alcohol solvents 27 ) consistent with a high barrier. Significantly however, this recovery is very environment sensitive, being greatly accelerated in aqueous solution, and by a single mutation in the protein.…”

Section: Resultsmentioning

confidence: 90%

“…Significantly however, this recovery is very environment sensitive, being greatly accelerated in aqueous solution, and by a single mutation in the protein. 18,27,28 This demonstrates a major role for the medium in modifying the chromophore isomerization coordinate, suggesting an environment sensitive barrier or reaction coordinate. To accelerate the isomerization reaction from hours to 91 ns requires a remarkable reduction in an activation barrier from 180 kJ mol −1 to < 30 kJ mol −1 , assuming in the latter case a pre-exponential frequency factor ( A ) of ca 10 13 s −1 .…”

Section: Resultsmentioning

confidence: 91%

Infrared spectroscopy reveals multi-step multi-timescale photoactivation in the photoconvertible protein archetype dronpa

et al. 2018

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Photochromic fluorescent proteins play key roles in super-resolution microscopy and optogenetics. The light-driven structural changes that modulate the fluorescence involve both trans-to-cis isomerization and proton transfer. The mechanism, timescale and relative contribution of chromophore and protein dynamics are currently not well understood. Here, the mechanism of off-to-on-state switching in dronpa is studied using femtosecond-to-millisecond time-resolved infrared spectroscopy and isotope labelling. Chromophore and protein dynamics are shown to occur on multiple timescales, from picoseconds to hundreds of microseconds. Following excitation of the trans chromophore, a ground-state primary product is formed within picoseconds. Surprisingly, the characteristic vibrational spectrum of the neutral cis isomer appears only after several tens of nanoseconds. Further fluctuations in protein structure around the neutral cis chromophore are required to form a new intermediate, which promotes the final proton-transfer reaction. These data illustrate the interplay between chromophore dynamics and the protein environment underlying fluorescent protein photochromism.

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“…The relevance of the MEPs increases in situations with low excess of kinetic energy, such as in vibrationally relaxed or “cold” excited states, where the system is forced to follow the path with the smallest energetic penalty. This approach has been widely used to study photoinduced mechanisms in organic and biochemical systems but relatively less used to study photoresponses in Fe(II) complexes.…”

Section: Potential Energy Surfacesmentioning

confidence: 99%

Toward Luminescent Iron Complexes: Unravelling the Photophysics by Computing Potential Energy Surfaces

et al. 2019

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Due to its high societal impact, the replacement of precious metals used in technological devices by more abundant and eco-friendly metals, such as iron, has stimulated significant scientific efforts in the last years. In the present review, we focus on different computational strategies and techniques used to characterize the potential energy surfaces (PESs) that govern the photophysical pathways of a wide variety of Fe II complexes. The different procedures are discussed in terms of accuracy, computational cost and availability of the implementations, and illustrated with specific examples taken from the literature. The determination of minimum energy paths (MEPs) and the optimization of minimum energy crossing points (MECPs) are particularly emphasized since they can be combined to provide connected and optimized PESs independent from any a priori selected coordinate. The use of such computational techniques is exemplified in detail through a recent study on the influence of the facial and meridional isomerism in the triplet PESs of a pyridylcarbene Fe(II) complex, and its implications in the decay mechanism of each isomer.

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A new twist in the photophysics of the GFP chromophore: a volume-conserving molecular torsion couple

Abstract: Dynamics of a nonplanar GFP chromophore are studied experimentally and theoretically. Coupled torsional motion is responsible for the ultrafast decay.

Cited by 39 publications

References 78 publications

Picosecond Switchable Azo Dyes

Picosecond Switchable Azo Dyes

Infrared spectroscopy reveals multi-step multi-timescale photoactivation in the photoconvertible protein archetype dronpa

Toward Luminescent Iron Complexes: Unravelling the Photophysics by Computing Potential Energy Surfaces

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