Intramolecular electron transfer in flavin adenine dinucleotide. Photochemically induced dynamic nuclear polarization study at high and low magnetic fields

Stob, S; Kemmink, Johan; Kaptein, Robert

doi:10.1021/ja00200a021

Cited by 29 publications

(29 citation statements)

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“…20 1 (R/R)* can generate the singlet excimer state, 1 (R-R)*, with rate constant k Sex . We also assumed that a close RP, [26][27][28][29] (R*/R), is formed, where eldsensitive ISC does not happen due to the energy gap between the S and the T 0 states resulting from non-negligible exchange interactions (Fig. 3d).…”

Section: Resultsmentioning

confidence: 99%

A ground-state-dominated magnetic field effect on the luminescence of stable organic radicals

Kimura

Kato

et al. 2021

Chem. Sci.

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Section: Resultsmentioning

confidence: 99%

A ground-state-dominated magnetic field effect on the luminescence of stable organic radicals

Kimura

Kato

et al. 2021

Chem. Sci.

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“…The low pH ensures protonation of the flavin which prevents flavin-adenine ring stacking in the ground state. 21…”

Section: Methodsmentioning

confidence: 99%

Broadband Cavity-Enhanced Detection of Magnetic Field Effects in Chemical Models of a Cryptochrome Magnetoreceptor

Neil

Sheppard

et al. 2014

J. Phys. Chem. B

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Broadband cavity-enhanced absorption spectroscopy (BBCEAS) is shown to be a sensitive method for the detection of magnetic field effects (MFEs) in two flavin-based chemical reactions which are simple models for cryptochrome magnetoreceptors. The advantages of optical cavity-based detection and (pseudo-white-light) supercontinuum radiation have been combined to provide full spectral coverage across the whole of the visible spectrum (425 < λ < 700 nm). This region covers the absorbance spectra of flavin mononucleotide (FMN) and flavin adenine dinucleotide (FAD) as well as their photogenerated radicals. To illustrate the power of this technique, BBCEAS has been used to record the spectral dependence of MFEs for photoinduced radical pairs formed in the intermolecular reaction of FMN with lysozyme and the intramolecular photochemistry of FAD. These reactions have been chosen for their photochemical similarities to cryptochrome proteins which have been proposed as key to the magnetic compass sense of many animals including birds. In experiments performed using low protein concentrations (10 μM) and 1 mm optical path-lengths, absorbance changes as small as 1 × 10(-7) (representing <0.1% MFEs) have been detected with good signal-to-noise offering the prospect of sensitive MFE detection in cryptochrome.

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“…This result agrees with previous publications. 11,42,[47][48][49] Compared to transient absorption, results of the fluorescence band integral analysis on FAD/water are less clear. In transient fluorescence, a biexponential function with 1.6 ps (32%) and 8.0 ps (46%) is needed to describe the intensity decay.…”

Section: Relaxation Of Excited Flavin Seen By Transientmentioning

confidence: 99%

Femtosecond Stimulated Raman Spectroscopy of Flavin after Optical Excitation

Weigel¹,

Dobryakov²,

Klaumünzer³

et al. 2011

J. Phys. Chem. B

143

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In blue-light photoreceptors using flavin (BLUF), the signaling state is formed already within several 100 ps after illumination, with only small changes of the absorption spectrum. The accompanying structural evolution can, in principle, be monitored by femtosecond stimulated Raman spectroscopy (FSRS). The method is used here to characterize the excited-state properties of riboflavin and flavin adenine dinucleotide in polar solvents. Raman modes are observed in the range 90-1800 cm(-1) for the electronic ground state S(0) and upon excitation to the S(1) state, and modes >1000 cm(-1) of both states are assigned with the help of quantum-chemical calculations. Line shapes are shown to depend sensitively on resonance conditions. They are affected by wavepacket motion in any of the participating electronic states, resulting in complex amplitude modulation of the stimulated Raman spectra. Wavepackets in S(1) can be marked, and thus isolated, by stimulated-emission pumping with the picosecond Raman pulses. Excited-state absorption spectra are obtained from a quantitative comparison of broadband transient fluorescence and absorption. In this way, the resonance conditions for FSRS are determined. Early differences of the emission spectrum depend on excess vibrational energy, and solvation is seen as dynamic Stokes shift of the emission band. The nπ* state is evidenced only through changes of emission oscillator strength during solvation. S(1) quenching by adenine is seen with all methods in terms of dynamics, not by spectral intermediates.

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Intramolecular electron transfer in flavin adenine dinucleotide. Photochemically induced dynamic nuclear polarization study at high and low magnetic fields

Cited by 29 publications

References 0 publications

A ground-state-dominated magnetic field effect on the luminescence of stable organic radicals

A ground-state-dominated magnetic field effect on the luminescence of stable organic radicals

Broadband Cavity-Enhanced Detection of Magnetic Field Effects in Chemical Models of a Cryptochrome Magnetoreceptor

Femtosecond Stimulated Raman Spectroscopy of Flavin after Optical Excitation

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