Direct Measurement of Photochromic Durability at the Single-molecule Level

Fukaminato, Tuyoshi; Umemoto, Tohru; Iwata, Yasuhide; Irie, Masahiro

doi:10.1246/cl.2005.676

Cited by 13 publications

(11 citation statements)

References 17 publications

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“…Therefore, compounds 4 - Et and 11 were not expected to be more photostable than compound 1b . A rough estimation of the average number of switching cycles may be based on the observation that SMs of fluorescent dyes (including photochromic fluorescent DAEs) generally decompose after 10 6 –10 7 excitation cycles. − If we consider the values of the isomerization quantum yields for one complete cycle (OF–CF–OF) of compounds 4-Et and 11 (Table ), we may estimate that the average number of switching cycles is expected to be on the order of ∼10. Evaluation of the fatigue resistance of compounds 4-Et and 11 in diluted methanolic and aqueous solutions showed that they can endure several tens of cycles (Figure S7).…”

Section: Resultsmentioning

confidence: 99%

Fluorescent Photoswitchable Diarylethenes for Biolabeling and Single-Molecule Localization Microscopies with Optical Superresolution

et al. 2017

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A modular assembly of water-soluble diarylethenes (DAEs), applicable as biomarkers for optical nanoscopy, is reported. Reversibly photoswitchable 1,2-bis(2-alkyl-6-phenyl-1-benzothiophene-1,1-dioxide-3-yl)perfluorocyclopentenes possessing a fluorescent "closed" form were decorated with one or two methoxy group(s) attached to the para-position(s) of phenyl ring(s) and two, four, or eight carboxylic acid groups. Antibody conjugates of these DAEs feature low aggregation, efficient photoswitching in aqueous buffers, specific staining of cellular structures, and photophysical properties (high emission efficiencies and low cycloreversion quantum yields) enabling their application in superresolution microscopy. Images of tubulin, vimentin, and nuclear pore complexes are presented. The superresolution images can also be acquired by using solely 488 nm light without additional photoactivation with UV light. These DAEs exhibit reversible photoswitching without requiring any additives to the imaging media and open new paths toward the modular design of fluorescent dyes for bioimaging with optical superresolution.

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Section: Resultsmentioning

confidence: 99%

Fluorescent Photoswitchable Diarylethenes for Biolabeling and Single-Molecule Localization Microscopies with Optical Superresolution

et al. 2017

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“…It was demonstrated that some carbocyanine dyes also act as efficient reversible photoswitches at the singlemolecule level upon irradiation with red and green light. 11, 12 Although the efficiency of photoswitching at the single-molecule level has been improved greatly in the past few years for the diarylethene derivatives, 13 it is still below the excellent values reported for the ensemble photochromic reaction. 14 Moreover, in the case of cabocyanine dyes, the mechanism of the photoswitching observed at the single-molecule level is not fully understood.…”

Section: Introductionmentioning

confidence: 99%

Photo-induced protonation/deprotonation in the GFP-like fluorescent protein Dronpa: mechanism responsible for the reversible photoswitching

Habuchi

Dedecker

Hotta

et al. 2006

Photochem Photobiol Sci

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Recently, reversible photoswitching in bulk samples or in individual molecules of Dronpa, a mutant of a green fluorescent protein (GFP)-like fluorescent protein, has been demonstrated. Intense irradiation at 488 nm changed Dronpa in a dim protonated form, and weak irradiation at 405 nm restored it to the bright deprotonated form. Here, we report on the mechanism of photoswitching of Dronpa by means of ensemble and single-molecule spectroscopy. Ensemble spectroscopy shows that the photoswitching can be described, in first approximation, by a three-state model including a deprotonated (B), a protonated (A1), and a photoswitched protonated (A2) forms of the chromophore. While the B and the A1 forms are in a ground state acid-base equilibrium, the B and the A2 forms are reversibly photoswitched upon irradiation with 488 and 405 nm light. At the single-molecule level, the on-times in fluorescence intensity trajectories excited at 488 nm decrease with increasing the excitation power, consistent with the photoswitching from the B to A2 form. The on-times agree well with expected values, which are calculated based on the ensemble spectroscopic properties of Dronpa. The fluorescence trajectory obtained with simultaneous dual-color excitation at 488 and 405 nm demonstrates reversible photoswitching between the B and the A2 forms at the single-molecule level. The efficiency of the photoswitching from the A2 to B form increased with increasing the excitation power of the 405 nm light. Our results demonstrate that Dronpa holds its outstanding photoswitching properties, based on a photo-induced protonation/deprotonation process, even at the single-molecule level.

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“…In addition, the ratio (contrast) between the emission intensity measured after the photochromic transformation and that measured before is related to the composition of the photostationary state. In most instances, both interconvertible forms are present at the photostationary state and, hence, these photoswitchable systems generally have modest contrast ratios with few notable exceptions. − In addition, their excitation dynamics can encourage competitive deactivation pathways and the gradual degradation of the fluorescent and/or photochromic components with the number of switching cycles. Thus, the evolution of these molecular and supramolecular switches into functional materials for practical applications requires the identification of innovative operating principles that would ensure fluorescence photoswitching with improved contrast ratios and fatigue resistances.…”

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Fluorescence Switching with a Photochromic Auxochrome

Deni̇z

Sortino

Raymo

2010

J. Phys. Chem. Lett.

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We synthesized a photoswitchable fluorescent probe incorporating a coumarin fluorophore and an oxazine photochrome within the same molecular skeleton. The visible illumination of this fluorophore−photochrome dyad results in the excitation of the fluorescent component only if the photochromic element is activated with ultraviolet irradiation. Indeed, the photoinduced opening of the oxazine ring bathochromically shifts the absorption of the coumarin fragment sufficiently to encourage its visible excitation with concomitant fluorescence. These operating principles translate into fluorescence photoactivation with good contrast ratio and brightness as well as short fluorescence lifetime. The modular character and relative simplicity of this synthetic strategy for the assembly of photoswitchable constructs might evolve into a general design logic for the photoregulation of the electronic structure of a given chromophore with a photochromic auxochrome.

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Direct Measurement of Photochromic Durability at the Single-molecule Level

Abstract: A fluorescent photochromic diarylethene, which has excellent photostability and efficient fluorescence switching character even at the single-molecule level, was synthesized and the fatigue resistant property was quantitatively evaluated.

Cited by 13 publications

References 17 publications

Fluorescent Photoswitchable Diarylethenes for Biolabeling and Single-Molecule Localization Microscopies with Optical Superresolution

Fluorescent Photoswitchable Diarylethenes for Biolabeling and Single-Molecule Localization Microscopies with Optical Superresolution

Photo-induced protonation/deprotonation in the GFP-like fluorescent protein Dronpa: mechanism responsible for the reversible photoswitching

Fluorescence Switching with a Photochromic Auxochrome

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