Multichromophoric Cyclodextrins. 6. Investigation of Excitation Energy Hopping by Monte-Carlo Simulations and Time-Resolved Fluorescence Anisotropy

Berberan‐Santos, Mário N.; Choppinet, Patricia; Fedorov, Alexander; Jullien, and Ludovic; Valeur, Bernard

doi:10.1021/ja983601n

Cited by 54 publications

(63 citation statements)

References 22 publications

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“…3c). The r N values are inversely proportional to the number of fluorophores involved in 36,37 , where r 0 is the fundamental anisotropy (0.37 for rhodamine B). Therefore, we can roughly estimate that for 1 and 5 wt% loading with R18/F5-TPB, around 40 and 200 fluorophores, respectively, were engaged in EET.…”

Section: Photophysics Of Nps In Solutionmentioning

confidence: 99%

Collective fluorescence switching of counterion-assembled dyes in polymer nanoparticles

et al. 2014

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The current challenge in the field of fluorescent nanoparticles (NPs) for bioimaging is to achieve extreme brightness and external control of their emission using biodegradable materials. Here we propose a new concept of fluorescent polymer NPs, doped with ionic liquid-like salts of a cationic dye (octadecyl rhodamine B) with a bulky hydrophobic counterion (fluorinated tetraphenylborate) that serves as spacer minimizing dye aggregation and self-quenching. The obtained 40-nm poly(D,L-lactide-co-glycolide) NPs containing up to 500 dyes are brighter than quantum dots and exhibit photo-induced reversible on/off fluorescence switching, never reported for dye-doped NPs. We show that this collective switching of hundreds of dyes is due to ultrafast excitation energy transfer and can be used for super-resolution imaging. These NPs, being spontaneously endocytosed by living cells, feature high signal-to-noise ratio and absence of toxicity. The counterion-based concept opens the way to a new class of nanomaterials for sensing, imaging and light harvesting.

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Section: Photophysics Of Nps In Solutionmentioning

confidence: 99%

Collective fluorescence switching of counterion-assembled dyes in polymer nanoparticles

et al. 2014

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“…Ionisable CDs were prepared such as for instance sulphobutylether-β-cyclodextrin. Exotic cyclodextrins were also synthetized for specific purposes: β-CD polymers [36], multichromophoric cyclodextrins [37] or bisnaphtylsulphonyl-βCD [38] and bis-pyrenyl-βCD [39] to detect organic compounds by a guest responsive monomer or excimer fluorescence. A similar solution was devised by Narita et al to sense endocrine-disrupting chemicals and their analogues by fluorescence pattern recognition.…”

Section: Modified Cyclodextrinsmentioning

confidence: 99%

Luminescence in organized media and supramolecular interactions:physicochemical aspects and applications

Lerner¹,

Martín²

2000

Analusis

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Introduction Molecular luminescence of analytes in organized media or in supramolecular complexes of cyclodextrinsThe photophysical and photochemical behaviour of molecules complexed to cyclodextrins (CD) is generally different from their behaviour in solution. The first observations in the field were qualitative and were related to the increased stabilisation of labile molecules, mostly drugs, against photodegradation when complexed to natural cyclodextrins [1]. Complexation by CD's was then the preferred subject for those involved in supramolecular chemistry and drug vectorisation techniques [2] as well as in separation techniques [3][4][5]. Stabilization of a molecule against photochemical degradation is still very important in the field of pharmaceutical sciences. A recent example is the stabilisation of promazine as an inclusion complex with β-cyclodextrin [6]. Other photochemists were attracted quite early to this field of research and initiated studies, which were mostly photophysical in nature [7,8]. The key observation was that the formation of supramolecular complexes of analytes with cyclodextrins (CDs) resulted in an increase of their fluorescence quantum yield or even in the appearance of room temperature phosphorescence (RTP) [9][10][11][12]. This enhancement has been used to increase the sensitivity and the selectivity in both luminescence and chromatographic techniques [13-15].We will not say more about RTP with CDs as the subject will be developed in another contribution in the same issue of this Journal. However RTP is also observed in the solubilization of analytes in micellar colloïdal solutions and this field will be reviewed hereunder.These properties have been used to develop analytical techniques, which combine the selectivity of complexation with an enhanced emission [16][17][18][19]. In this way an improvement in the detection limits is obtained in many separation techniques such as HPLC, capillary electrophoresis (CE) or planar chromatography. Furthermore these molecular interactions allow to reveal or to stabilize new molecular forms or to turn species which are normally non-emitting into luminescent ones. All these aspects are reviewed hereunder after a short summary on the nature of the intermolecular interactions, which lie at the heart of these effects. Nature of the interactions between an analyte and a CD or a micelleWithout going into a thorough analysis of the origin of the interactions which exist between molecules in dense media which concern us here, it seems useful to recall the most important factors which should be taken into account when any type of luminescence, fluorescence or phosphorescence is involved.

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“…16 At a lower level of molecular complexity, relatively simple bichromophore, donor-acceptor molecules provide environments within which energy migration is readily observed; such molecules have been the subject of a number of reviews. [17][18][19] Notable amongst more complex, multichromophore systems are cyclodextrins 20,21 and other multiporphyrin arrays. [22][23][24] Dendrimers also feature prominently in recent research; these highly branched macromolecules comprise chromophores linked in fractal or other highly symmetric geometries 25 and much interest has focused upon energy transfer from their dendritic constituents to photoactive cores.…”

Section: Introductionmentioning

confidence: 99%

Resonance energy transfer: The unified theory revisited

Daniels

Jenkins

Andrews

2003

The Journal of Chemical Physics

146

131

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Resonance energy transfer ͑RET͒ is the principal mechanism for the intermolecular or intramolecular redistribution of electronic energy following molecular excitation. In terms of fundamental quantum interactions, the process is properly described in terms of a virtual photon transit between the pre-excited donor and a lower energy ͑usually ground-state͒ acceptor. The detailed quantum amplitude for RET is calculated by molecular quantum electrodynamical techniques with the observable, the transfer rate, derived via application of the Fermi golden rule. In the treatment reported here, recently devised state-sequence techniques and a novel calculational protocol is applied to RET and shown to circumvent problems associated with the usual method. The second-rank tensor describing virtual photon behavior evolves from a Green's function solution to the Helmholtz equation, and special functions are employed to realize the coupling tensor. The method is used to derive a new result for energy transfer systems sensitive to both magnetic-and electric-dipole transitions. The ensuing result is compared to that of pure electric-dipoleelectric-dipole coupling and is analyzed with regard to acceptable transfer separations. Systems are proposed where the electric-dipole-magnetic-dipole term is the leading contribution to the overall rate.

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Multichromophoric Cyclodextrins. 6. Investigation of Excitation Energy Hopping by Monte-Carlo Simulations and Time-Resolved Fluorescence Anisotropy

Cited by 54 publications

References 22 publications

Collective fluorescence switching of counterion-assembled dyes in polymer nanoparticles

Collective fluorescence switching of counterion-assembled dyes in polymer nanoparticles

Luminescence in organized media and supramolecular interactions:physicochemical aspects and applications

Resonance energy transfer: The unified theory revisited

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