Ultrafast Vibrational Spectroscopic Studies on the Photoionization of the α-Tocopherol Analogue Trolox C

Parker, Anthony W.; Bisby, Roger H.; Greetham, Gregory M.; Kukura, Philipp; Scherer, Kathrin M.; Towrie, Michael

doi:10.1021/jp505113k

Cited by 5 publications

(7 citation statements)

References 43 publications

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“…Armed with this knowledge, future rational design of MAMs which retain charge transfer character in protic solvents but prevent EDPT, and thus fluorescence quenching, would yield an extremely powerful fluorescent probe. Furthermore, proton loss and proton transfer mechanisms have been shown to be crucial in vital processes such as radical scavenging in vitamin E. 76 Small, single molecule MAM fluorophores such as the one discussed here could prove instrumental in probing such mechanisms within living cells. We thus consider the present work as a platform for exploration into the hitherto unexploited and far-reaching potential of MAM chromophores, launching exciting research opportunities into such fields as two-photon absorption fluorescence imaging with MAMs, modification of MAMs to reduce absorption onset energy,…”

Section: Discussionmentioning

confidence: 96%

First Step toward a Universal Fluorescent Probe: Unravelling the Photodynamics of an Amino–Maleimide Fluorophore

et al. 2017

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Continuous advancements in biophysics and medicine at the molecular level make the requirements to image structure-function processes in living cells ever more acute. While fluorophores such as the green fluorescent protein have proven instrumental toward such efforts, the advent of nondiffraction limited microscopy limits the utility of such fluorescent tags. Monoaminomaleimides are small, single molecule fluorophores that have been shown to possess stark variations in their emission spectra in different solvent environments, making them a potentially powerful tool for a myriad of applications. The ability to "autotune" fluorescence according to different media allows for a probe capable of working in all regions of a cell, or accurately characterizing the purity of an environment. In this work, we present ultrafast pump-probe studies of a model monoaminomaleimide, 1-methyl-3-(methylamino)-1H-pyrrole-2,5-dione, and demonstrate how fluorescence quenching in polar protic solvents is caused by electron driven proton transfer from the solvent to the fluorophore. Armed with this knowledge, the present study acts as a first step for the rational design of future maleimides, potentially moving toward creating a universal fluorophore with tunable efficiency, dependent on environment.

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Section: Discussionmentioning

confidence: 96%

First Step toward a Universal Fluorescent Probe: Unravelling the Photodynamics of an Amino–Maleimide Fluorophore

et al. 2017

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“…However, for maximum signal the polarizations are usually chosen parallel. Rotational diffusion artifacts arising from impulsive excitation with the actinic pump pulse, which become an issue for time delays above a few ps, can be eliminated by setting the actinic polarization to the magic angle (54.7°) . On the other hand, to maximize the signal from impulsively excited wavepackets at early times, the actinic and probe polarizations are usually chosen to be parallel .…”

Section: Methodsmentioning

confidence: 99%

“…Other examples of isomerization reactions investigated so far include stilbene, 1,1′‐diethyl‐2,2′‐pyridocyanine, 4‐nitro‐4′‐dimethylamino‐azobenzene, vitamin E, azobenzene, and acetylbenzaldehyde . Trans‐stilbene has also been used as a model compound to study solvent‐induced vibrational cooling and heating dynamics …”

Section: Systems and Applicationsmentioning

confidence: 99%

Femtosecond Stimulated Raman Spectroscopy

2016

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Femtosecond stimulated Raman spectroscopy (FSRS) is an ultrafast nonlinear optical technique that provides vibrational structural information with high temporal (sub-50 fs) precision and high spectral (10 cm(-1) ) resolution. Since the first full demonstration of its capabilities ≈15 years ago, FSRS has evolved into a mature technique, giving deep insights into chemical and biochemical reaction dynamics that would be inaccessible with any other technique. It is now being routinely applied to virtually all possible photochemical reactions and systems spanning from single molecules in solution to thin films, bulk crystals and macromolecular proteins. This review starts with an historic overview and discusses the theoretical and experimental concepts behind this technology. Emphasis is put on the current state-of-the-art experimental realization and several variations of FSRS that have been developed. The unique capabilities of FSRS are illustrated through a comprehensive presentation of experiments to date followed by prospects.

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“…1−7 A great variety of ultrafast chemical reactions have been studied ranging from excited-state proton transfer, 3,8−10 isomerization, 2,11 charge transfer, 12−15 internal conversion, 5,16 and bond dissociation. 17,18 In brief, the typical FSRS technique employs three pulses: an actinic pump initiates photochemistry by creating a population and sometimes coherence in an electronic excited state, followed by a narrowband Raman pump and broadband probe pair which generates the stimulated Raman scattering photon. 1,19,20 The broadband probe simultaneously samples vibrational modes in a wide spectral range (ca.…”

Section: Introductionmentioning

confidence: 99%

Dynamic Raman Line Shapes on an Evolving Excited-State Landscape: Insights from Tunable Femtosecond Stimulated Raman Spectroscopy

et al. 2017

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Tracking molecular motions in real time remains a formidable challenge in science and engineering fields because the experimental methodology requires simultaneously high spatial and temporal resolutions. Building on early successes and future potential of femtosecond stimulated Raman spectroscopy (FSRS) as a structural dynamics technique, we present a comprehensive study of stimulated Raman line shapes of a photosensitive molecule in solution with tunable Raman pump and probe pulses. Following femtosecond 400 nm electronic excitation, the model photoacid pyranine exhibits dynamic and mode-dependent Raman line shapes when the Raman pump is tuned from the red side toward and across the excited-state absorption (ESA) band (e.g., from S1) with varying resonance conditions. On the anti-Stokes FSRS side, low-frequency modes below ∼1000 cm–1 exhibit a line shape change from gain to dispersive to loss, whereas the dispersive intermediate is much less notable for high-frequency modes. The characteristic mode frequency blue shift involving vibrationally hot states in S1 with time constants of ∼9.6 and 58.6 ps reveals the sensitivity of anti-Stokes FSRS to vibrational cooling and solvation. This work lays the foundation for expanding tunable FSRS technology on both the Stokes and anti-Stokes sides to investigate a variety of photoinduced processes in solution with sufficient resolution to expose functional motions and increased sensitivity to monitor vibrational cooling.

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Ultrafast Vibrational Spectroscopic Studies on the Photoionization of the α-Tocopherol Analogue Trolox C

Cited by 5 publications

References 43 publications

First Step toward a Universal Fluorescent Probe: Unravelling the Photodynamics of an Amino–Maleimide Fluorophore

First Step toward a Universal Fluorescent Probe: Unravelling the Photodynamics of an Amino–Maleimide Fluorophore

Femtosecond Stimulated Raman Spectroscopy

Dynamic Raman Line Shapes on an Evolving Excited-State Landscape: Insights from Tunable Femtosecond Stimulated Raman Spectroscopy

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