Saturable absorption dynamics in the triplet system and triplet excitation induced singlet fluorescence of some organic molecules

Gratz, H.; Penzkofer, Alfons

doi:10.1016/s0301-0104(00)00355-4

Cited by 15 publications

(17 citation statements)

References 59 publications

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“…Multi‐step photobleaching is extremely pronounced for Eosin Y and 2‐bromo‐fluorescein, which are known for their large ISC yield 21. 22 In contrast, we observed a slight instantaneous increase in fluorescence signal for EYFP (Figure 6 c). Again, this increase in fluorescence signal was not due to direct excitation by 671 nm as sole excitation by 671 nm did not elicit a noticeable signal.…”

Section: Resultsmentioning

confidence: 66%

“…From T n the dye can efficiently cross back to the singlet system, where fluorescence emission occurs 17–20. ReISC has previously been shown for dyes with high ISC yields such as bipyridien,17 erythrosine B,18, 21, 22 rose bengal,18, 21–25 cyanine dyes,19, 20 anthracene,26 eosin Y21, 22 and propiophenone 27. ReISC had to be included in fluorescence statistics of single‐molecule experiments of sulforhodamine 101 or DiI in polymethylmethacrylat (PMMA),28 terrylene in p ‐terphenyl crystals,29 merocyanine 540 in solution,30 and of cyanine 5 (Cy5) in poly(vinyl‐alcohol) (PVA),31 on air‐glass interfaces,32 under nitrogen atmosphere33 or in Förster resonance energy transfer (FRET) experiments 34.…”

Section: Introductionmentioning

confidence: 99%

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Enhancing Fluorescence Brightness: Effect of Reverse Intersystem Crossing Studied by Fluorescence Fluctuation Spectroscopy

et al. 2008

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Experiments based on fluorescence detection are limited by the population of the fluorescence marker's long-lived dark triplet state, leading to pronounced photobleaching reactions and blinking which reduces the average fluorescence signal obtained per time interval. By irradiation with a second, red-shifted laser line, we initiate reverse intersystem crossing (ReISC) which enhances the fluorescence signal of common fluorophores up to a factor of 14. The reverse intersystem crossing from the triplet state back to the singlet system is achieved by photoexcitation to higher-excited triplet states, which are, however, prone to photobleaching. We gain insights into the competing pathways of ReISC and photobleaching. The relative efficiencies of these two pathways and the triplet lifetime determine the achievable fluorescence enhancement, which varies strongly with the choice of dye, excitation irradiance and wavelength, and with environmental conditions. The study of ReISC not only results in a better understanding of a fluorescent label's photophysics, but the method is a possible approach to optimize fluorescence emission in experiments, where signal strength is a critical parameter.

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Section: Resultsmentioning

confidence: 66%

Section: Introductionmentioning

confidence: 99%

Enhancing Fluorescence Brightness: Effect of Reverse Intersystem Crossing Studied by Fluorescence Fluctuation Spectroscopy

et al. 2008

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“…The very high intersystem crossing rate of rose bengal, for example enables low primary-laser excitation to yield strong enhancement, but must be coupled with high intensity secondary-laser illumination. Although both eosin Y and erythrosin B have significant triplet quantum yields (56%34 and 90%,34 respectively), they are much lower than for rose bengal (98%) 38,40. This enables brighter overall emission but results in lower enhancement levels to be observed.…”

Section: Resultsmentioning

confidence: 96%

Synchronously Amplified Fluorescence Image Recovery (SAFIRe)

2009

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Fluorescence intermittency severely limits brightness in both single molecule and bulk fluorescence. Herein, we demonstrate that optical depopulation of organic fluorophore triplet states opens a path to significantly increased sensitivity by simultaneously increasing brightness and greatly reducing background through synchronously-detected fluorescence modulation. Image recovery is achieved through selective fluorescence enhancement via modulating a secondary laser excitation at much lower energy than the observed emission in order to depopulate the long-lived triplet states. A series of xanthene dyes that exhibit efficient triplet-state formation demonstrate that this method of selective signal extraction can be achieved at moderate primary and secondary excitation intensities through tailoring dye photophysics and imaging conditions. Up to 5-fold increases in solution-based fluorescence over primary laser excitation alone was achieved upon secondary laser excitation, and dynamic control of signal modulation was demonstrated over a wide time range simply by varying the modulation frequency of the laser used for depopulation of the triplet state. We identify the photophysical characteristics that enable existing or to-be-designed fluorophores to be used in Synchronously Amplified Fluorescence Image Recovery (SAFIRe) Microscopy.

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“…Quinones usually absorb ultra-violet light and undergo fast intersystem crossing from singlet to triplet state with high efficiency [6]. Among xanthene derivatives, erythrosin is known for its high quantum yield of triplet formation (the value of fluorescence quantum yield of erythrosin in aqueous solution is 0.02 [7]) with fast singlet to triplet intersystem crossing rate [8,9]. Photo-reduction of erythrosin studied by time resolved techniques have shown that Ery 3− is formed as a result of electron transfer reaction [7].…”

Section: Introductionmentioning

confidence: 99%

A Mechanistic Study of Photoinduced Electron Transfer from Triplet Erythrosin to Various Quinones Using Time Resolved Absorption and ESR-CIDEP Measurements

Mansha¹,

Asim²,

Grampp

et al. 2014

Zeitschrift Für Physikalische Chemie

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Photoinduced electron transfer reactions from the triplet erythrosin (Ery 2− ) dianion to various quinones (1,4-benzoquinone, 2,5-di-t-butyl-1,4-benzoquinone, duroquinone, 2,5-dichloro-1,4-benzoquinone, chloranil, bromanil, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and 9,10-anthraquinone) and other organic acceptors like 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane and with tetracyano-1,4-benzoquinone (cyanil), one of the strongest oxidizing agent reported in literature ( ∘ = 0.90 V vs. SCE), were studied by laser flash photolysis in acetonitrile/water mixtures at room temperature. Quenching rate constants are obtained from Stern-Volmer plots. The measured bimolecular quenching rate constants are close to the diffusion controlled rates. Excitation of a contact radical-pair or a triplet exciplex as an intermediate in the photoinduced electron transfer reaction in a slightly polar solvent (1-propanol) is confirmed by the observation of the net absorptive chemically induced dynamic electron polarization (CIDEP) spectra. The unusual net-absorptive CIDEP spectrum is explained by spin-orbit coupling interactions due to presence of four iodine atoms in the structure of erythrosin (heavy atom effect). The dependence of the electron transfer rate constants, et , on the driving force, Δ et is slightly parabolic and indicates the Marcus Inverted Region.

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Saturable absorption dynamics in the triplet system and triplet excitation induced singlet fluorescence of some organic molecules

Cited by 15 publications

References 59 publications

Enhancing Fluorescence Brightness: Effect of Reverse Intersystem Crossing Studied by Fluorescence Fluctuation Spectroscopy

Enhancing Fluorescence Brightness: Effect of Reverse Intersystem Crossing Studied by Fluorescence Fluctuation Spectroscopy

Synchronously Amplified Fluorescence Image Recovery (SAFIRe)

A Mechanistic Study of Photoinduced Electron Transfer from Triplet Erythrosin to Various Quinones Using Time Resolved Absorption and ESR-CIDEP Measurements

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