Fluorescence lifetimes of rhodamine dyes in vacuo

Nagy, Andrea M.; Talbot, F.; Czar, Martin F.; Jockusch, Rebecca A.

doi:10.1016/j.jphotochem.2012.06.017

Cited by 46 publications

(51 citation statements)

References 85 publications

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“…The measured time decays were both well‐fit by single exponential functions, as seen by the residuals, with τ F =3.80±0.05 ns for AOH + , and τ F =4.6±0.2 ns for AOH + ‐CB7. The stated uncertainties are ±three‐times the standard deviation of the fit, which we find to be a good empirical measure of the uncertainty based on previous measurements 71. The measured lifetimes were found to be invariant upon excitation at 470 and at 445 nm.…”

Section: Resultssupporting

confidence: 65%

“…By these arguments, the radiative decay rate in the gas phase is expected to be roughly half that in the aqueous phase. While this effect could contribute to a significant lengthening of the fluorescence lifetime in the gas phase for dyes with a high quantum yield,71 it is not sufficient to explain the magnitude of the observed effect for acridine orange, given that k nr ≫ k r .…”

Section: Resultsmentioning

confidence: 99%

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Understanding Photophysical Effects of Cucurbituril Encapsulation: A Model Study with Acridine Orange in the Gas Phase

Czar

Jockusch

2013

ChemPhysChem

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Encapsulation of dyes by cucurbituril macrocycles has proven profitable as a strategy to alter fluorescence characteristics in useful ways. Encapsulation generally results in longer fluorescence lifetimes, enhanced brightness, and solvatochromic effects not normally seen in the condensed phase. These effects have been attributed variously to both the removal of interactions with solvent molecules and to the confined environment of extremely low polarizability provided by the cucurbituril interior. It is difficult to disentangle these effects in solution. Here, we present results from gas-phase experiments designed to separate these effects, using cucurbit[7]uril (CB7), and the cationic dye acridine orange (AOH(+)) as a probe. Fluorescence properties of gaseous AOH(+) are compared with those of the gaseous AOH(+)-CB7 complex and with the properties of the dye and complex in aqueous solution. The dependence on the local environment of several spectroscopic properties is discussed, including the fluorescence excitation and emission maxima, the size of the Stokes shift, fluorescence lifetime and relative brightness. An understanding of the modulation of fluorescence properties by the local environment, such as that promoted by this work, will aid in the rational design of improved fluorophores and fluorescent sensors.

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Section: Resultssupporting

confidence: 65%

Section: Resultsmentioning

confidence: 99%

Understanding Photophysical Effects of Cucurbituril Encapsulation: A Model Study with Acridine Orange in the Gas Phase

Czar

Jockusch

2013

ChemPhysChem

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“…First, the action spectrum of (rh575) + ions indicates that fluorescence from the excited state occurs on a shorter time scale than either photofragmentation or internal vibrational redistribution (IVR), which is in full agreement with the high fluorescence quantum yield and a fluorescence lifetime of 5.65 ± 0.04 ns in vacuo. 47 Second, the high fragmentation yields observed in (AAK−QSY7) + and the large difference in the observed fragmentation following CID and LID indicates that photofragmentation of (QSY7) + occurs on a shorter time scale than IVR. Finally, the observation of FRET in (rh575−AAK− QSY7) 2+ indicates that FRET must occur on a shorter time scale than fluorescence of (rh575) + , and again that the subsequent photofragmentation of (QSY7) + must occur on a shorter time scale than IVR.…”

Section: ■ Results and Discussionmentioning

confidence: 97%

Action-FRET: Probing the Molecular Conformation of Mass-Selected Gas-Phase Peptides with Förster Resonance Energy Transfer Detected by Acceptor-Specific Fragmentation

et al. 2014

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The use of Forster resonance energy transfer (FRET) as a probe of the structure of biological molecules through fluorescence measurements in solution is well-attested. The transposition of this technique to the gas phase is appealing since it opens the perspective of combining the structural accuracy of FRET with the specificity and selectivity of mass spectrometry (MS). Here, we report FRET results on gasphase polyalanine ions obtained by measuring FRET efficiency through specific photofragmentation rather than fluorescence. The structural sensitivity of the method was tested using commercially available chromophores (QSY 7 and carboxyrhodamine 575) grafted on a series of small, alanine-based peptides of differing sizes. The photofragmentation of these systems was investigated through action spectroscopy, and their conformations were probed using ion mobility spectrometry (IMS) and Monte Carlo minimization (MCM) simulations. We show that specific excitation of the donor chromophore results in the observation of fragments that are specific to the electronic excitation of the acceptor chromophore. This shows that energy transfer took place between the two chromophores and hence that the action-FRET technique can be used as a new and sensitive probe of the structure of gas-phase biomolecules, which opens perspectives as a new tool in structural biology.F orster resonance energy transfer (FRET) is a widely used probe of molecular structure in solution. 1−4 It requires a photon source to electronically excite the so-called "donor chromophore" and a light-harvesting setup to detect either the "donor" or "acceptor" chromophore fluorescence. The occurrence of FRET is then usually evidenced through a decrease in the fluorescence of the donor chromophore (quenching), with the concurrent onset of the fluorescence of the acceptor chromophore or by changes in fluorescence decay times. The interpretation of FRET results relies on the known distance dependence of the effect and on the possibility to graft specific chromophores at relatively well-defined sites on a molecule. FRET is then used to characterize the distance between the chromophores and hence separation between the grafting sites, although extracting exact distances is difficult due to the uncertainty of the exact orientation of the transition dipole moments of the chromophores. This allows the use of FRET to probe intra-or intermolecular distances, especially the change in distance, depending on whether the chromophores are attached to the same or to different molecules.The versatility of FRET makes it a powerful tool to assess the conformation and/or association of molecules. It has been shown that the overall structure of complex molecular edifices can be preserved in the gas phase using soft ionization techniques. 5,6 Therefore, the development of techniques capable of probing FRET in the gas phase is of high interest and could be integrated into a global approach for structure determination of proteins and protein complexes. 7−9 There are few tec...

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“…For example, time-resolved fluorescence anisotropy (TR-FA) and imaging have enabled the direct probing of biophysical processes, [1][2][3] while alignment experiments in the gas-phase have opened up countless avenues for probing molecular-frame processes. [4][5][6] Some of the experimental tools are transferable between solution and gas phases and fluorescence measurements have elegantly demonstrated their potential power in large isolated molecular systems, [7][8][9][10][11][12][13][14] including distance measurements using Förster resonance energy transfer. [14][15][16][17][18][19][20] TR-FA in particular has been very informative in biophysics and consequently, it also has great potential to become an important analytical tool in structure and function determination in the gas-phase, however, this premise has yet to be fully realized.…”

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confidence: 99%

Time-Resolved Photodetachment Anisotropy: Gas-Phase Rotational and Vibrational Dynamics of the Fluorescein Anion

Horke

Chatterley²,

Bull

et al. 2014

J. Phys. Chem. Lett.

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. (2015) 'Time-resolved photodetachment anisotropy : gas-phase rotational and vibrational dynamics of the uorescein anion.', Journal of physical chemistry letters., 6 (1). pp. 189-194. Further information on publisher's website: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details.

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Fluorescence lifetimes of rhodamine dyes in vacuo

Cited by 46 publications

References 85 publications

Understanding Photophysical Effects of Cucurbituril Encapsulation: A Model Study with Acridine Orange in the Gas Phase

Understanding Photophysical Effects of Cucurbituril Encapsulation: A Model Study with Acridine Orange in the Gas Phase

Action-FRET: Probing the Molecular Conformation of Mass-Selected Gas-Phase Peptides with Förster Resonance Energy Transfer Detected by Acceptor-Specific Fragmentation

Time-Resolved Photodetachment Anisotropy: Gas-Phase Rotational and Vibrational Dynamics of the Fluorescein Anion

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