Kinetic studies of intramolecular excimer formation in dipyrenylalkanes

Snare, M. J.; Thistlethwaite, Peter; Ghiggino, K. P.

doi:10.1021/ja00348a060

Cited by 99 publications

(125 citation statements)

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“…The first study of intramolecular pyrene excimer formation was reported by Zachariasse in 1976 for a series of n-alkanes terminated at both ends with a 1-pyrenemethyl group [151]. It was followed by numerous others that provided information about the ensemble of conformations adopted by the short alkane chain as it folds to bring its two ends in close proximity to form an excimer [152][153][154][155][156][157][158][159][160]. The scope of these studies was then expanded to include the end-to-end cyclization (EEC) of polymer chains by covalently attaching a pyrenyl group at both ends of a series of poly(ethylene oxide) (Py 2 -PEO) [78].…”

Section: Analysis Of the Kinetics Of Excimer Formation For Pyrene-labmentioning

confidence: 99%

Internal Dynamics of Dendritic Molecules Probed by Pyrene Excimer Formation

Duhamel

2012

Polymers

147

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Abstract:This review exposes the current poor understanding of the internal segmental chain dynamics of dendrimers in solution probed by monitoring the process of excimer formation between pyrene labels covalently attached to the chain ends of dendrimers. The review begins by covering the bases of fluorescence and the kinetics of pyrene excimer formation before describing a procedure based on the Model Free (MF) analysis that is used to analyze quantitatively the fluorescence decays acquired for dendrimers, the ends of which have been fully and covalently labeled with pyrene. Comparison of the various trends obtained by different research groups describing the efficiency of pyrene excimer formation with the generation number of dendrimers illustrates the lack of consensus between the few studies devoted to the topic. One possible reason for this disagreement might reside in the presence of minute amounts of unattached pyrene labels which act as potent fluorescent impurities and affect the analysis of the fluorescence spectra and decays in an uncontrolled manner. The review points out that the MF analysis of the fluorescence decays acquired with pyrene-labeled dendrimers enables one to account for the presence of unattached pyrene and to retrieve information about the internal segmental dynamics of the dendrimer. It provides guidelines that should enable future studies on pyrene-labeled dendrimers to yield results that are more straightforward to interpret.

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Section: Analysis Of the Kinetics Of Excimer Formation For Pyrene-labmentioning

confidence: 99%

Internal Dynamics of Dendritic Molecules Probed by Pyrene Excimer Formation

Duhamel

2012

Polymers

147

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“…All solutions show single exponential decay curves; the decay times are around 100 ns. It is well known that the fluorescence lifetime of pyrene is around 311 -400 ns in several organic solutions 22 and 200 ns in aqueous solution. 23 These results indicate that the fluorescence lifetime of 1-methylpyrene is shorter than that of pyrene.…”

Section: Apparatusmentioning

confidence: 99%

Effects of Cyclodextrins on Intramolecular Photoinduced Electron Transfer in a Boronic Acid Fluorophore

et al. 2014

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An inclusion complex consisting of a boronic acid fluorophore (C1-APB) and β-cyclodextrin (β-CyD) acts as a supramolecular sugar sensor whose response mechanism is based on photoinduced electron transfer (PET) from the excited pyrene to the boronic acid. We have investigated the PET process in C1-APB/CyD complexes by using time-resolved photoluminescence (TRPL) measurements at room temperature, and have succeeded in estimating the electron-transfer time to be about 1 ns. We have also studied the effects of CyDs on the PET process by comparing two kinds of CyDs (α-CyD, β-CyD) under different water-dimethyisulfoxide (DMSO) concentration conditions. We found that the CyDs interacting with the boronic acid moiety completely inhibits PET quenching and increases the monomer fluorescence intensity.Keywords Sugar recognition, time-resolved photoluminescence measurements, photoinduced electron transfer, cyclodextrin

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“…[19,21,40,52,[54][55][56][57][58] In addition to a usual structured monomer fluorescence band, the emission spectra of these compounds exhibit a broad and structureless band with maximum intensity in the vicinity of 450-500 nm due to fluorescence from an intramolecular excimer. [54,55] Pyrene is especially suitable for this purpose mainly because of the large stabilization energy of pyrene excimers (ca. 0.34 eV in cyclohexane) as well as the fact that pyrene and its derivatives possess fluorescence lifetimes long enough to achieve a suitable configuration for excimer formation.…”

Section: 3-bis(1-pyrenyl)propane I E /I Mmentioning

confidence: 99%

“…[55] Intramolecular excimer emission is strongest for dipyrenylpropane, which has been used as a fluorescent probe for micellar interiors. [54][55][56][57] Table 4 lists the intramolecular excimer-to-monomer (ca. 373 nm) emission intensity ratios (I E /I M ) for 1,3-bis(1- pyrenyl)propane dissolved in pH 4, 7, and 10 aqueous PSMADVE solutions, in 10 mM SDS solution, and also in selected neat organic solvents ( Figure 8 shows the emission spectra of 1,3-bis(1-pyrenyl)propane within aqueous PSMADVE solutions at pH 4, 7, and 10).…”

Section: 3-bis(1-pyrenyl)propane I E /I Mmentioning

confidence: 99%

Characterization of Solvation Environment Provided by Dilute Poly(sulfonyl maleic anhydride‐co‐dodecyl vinyl ether) Solutions at Various pH Using Pyrene and 1,3‐Bis(1‐pyrenyl)propane as Fluorescence Probes

Pandey

Redden

Fletcher

et al. 2003

Macro Chemistry & Physics

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Solubilization environments afforded by dilute aqueous solutions of poly(sulfonyl maleic anhydride‐co‐dodecyl vinyl ether) [PSMADVE, 1 wt.‐%] at pH 4, 7, and 10 are investigated using pyrene and 1,3‐bis(1‐pyrenyl)propane as fluorescence probes. While pyrene is a common polarity probe, intramolecular excimer formation in 1,3‐bis(1‐pyrenyl)propane makes it an interesting cybotactic region microviscosity probe. Results for pyrene II/IIII indicate that the most hydrophobic solubilization site is afforded at pH 4 followed by pH 10 and pH 7. The dipolarity indicated by pyrene is similar to that observed in m‐ and o‐xylene, toluene, and butyl benzoate. The solvation microenvironment afforded by the PSMADVE solutions is more hydrophobic than that observed within sodium dodecyl sulfate micellar solution. Additionally, further investigation of the relative size of the solubilization site revealed that the polymer solutions promoted intermolecular pyrene excimer formation at relatively low pyrene concentrations, indicating the possibility of localized concentration enhancement within the solvation pockets and/or compartmentalization of the solute molecules. This observation was most prominent at pH 10 and least at pH 7. 1,3‐Bis(1‐pyrenyl)propane intramolecular excimer formation efficiency at pH 4 is slightly higher than that for neat ethylene glycol, while at pH 10 is similar to that observed in 1‐octanol or dimethyl sulfoxide. Anomalously high excimer‐to‐monomer intensity ratio at pH 7 could be due to probe ground state heterogeneity, i.e., the existence of probe moieties in the ground state where the two pyrenyl groups are already aggregated. This is demonstrated by the fluorescence excitation data. Presence of the ground state aggregated form may give rise to anomalously high excimer formation efficiency.

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Kinetic studies of intramolecular excimer formation in dipyrenylalkanes

Cited by 99 publications

References 1 publication

Internal Dynamics of Dendritic Molecules Probed by Pyrene Excimer Formation

Internal Dynamics of Dendritic Molecules Probed by Pyrene Excimer Formation

Effects of Cyclodextrins on Intramolecular Photoinduced Electron Transfer in a Boronic Acid Fluorophore

Characterization of Solvation Environment Provided by Dilute Poly(sulfonyl maleic anhydride‐co‐dodecyl vinyl ether) Solutions at Various pH Using Pyrene and 1,3‐Bis(1‐pyrenyl)propane as Fluorescence Probes

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