Temperature dependence of excimer formation and excimer fluorescence polarization of micellar dispersions: surfactants as intrinsic probes

1984 ◽  
Vol 88 (21) ◽  
pp. 5008-5012 ◽  
Author(s):  
M. Aoudia ◽  
Michael A. J. Rodgers ◽  
W. H. Wade
Polymers ◽  
2021 ◽  
Vol 13 (11) ◽  
pp. 1690
Author(s):  
Weize Yuan ◽  
Remi Casier ◽  
Jean Duhamel

The denaturation undergone by α–helical poly(L-glutamic acid) (PLGA) in N,N-dimethylformamide upon addition of guanidine hydrochloride (GdHCl) was characterized by comparing the fluorescence of a series of PLGA constructs randomly labeled with the dye pyrene (Py-PLGA) to that of a series of Py-PDLGA samples prepared from a racemic mixture of D,L-glutamic acid. The process of pyrene excimer formation (PEF) was taken advantage of to probe changes in the conformation of α–helical Py-PLGA. Fluorescence Blob Model (FBM) analysis of the fluorescence decays of the Py-PLGA and Py-PDLGA constructs yielded the average number (<Nblob>) of glutamic acids located inside a blob, which represented the volume probed by an excited pyrenyl label. <Nblob> remained constant for randomly coiled Py-PDLGA but decreased from ~20 to ~10 glutamic acids for the Py-PLGA samples as GdHCl was added to the solution. The decrease in <Nblob> reflected the decrease in the local density of PLGA as the α–helix unraveled in solution. The changes in <Nblob> with GdHCl concentration was used to determine the change in Gibbs energy required to denature the PLGA α–helix in DMF. The relationship between <Nblob> and the local density of macromolecules can now be applied to characterize the conformation of macromolecules in solution.


Observations have been made of the concentration dependence of the fluorescence spectra of solutions of 1:2-benzanthracene and fifteen of its hydrocarbon derivatives. All of the compounds, except the 9,10-dim ethyl derivative, exhibit dim er emission at higher concentrations. The lower excited states, 1 L b and 1 L a , satisfy Förster’s conditions for fluorescent dim er formation. The factors determining the relative quantum yield of excimer fluorescence are discussed. The different types of crystal fluorescence spectra shown by the compounds are explained in terms of excimer formation in the crystal lattice.


The rate parameters of solvent-solute energy transfer and of oxygen-solvent quenching have been determined for solutions of 2, 5-diphenyloxazole in benzene, toluene, p -xylene and mesitylene. The role of excited molecules and excimers in transfer to the solute molecules is considered in terms of the Voltz relations, which include the Förster critical transfer distance, the molecular diffusion coefficients, and the solvent excitation migration coefficient. It is proposed that the migration is due to excimer formation and dissociation, and that the energy transfer occurs by a diffusion/migration-controlled collisional process. Dilution of the solvent decreases the migration, but increases the transfer distance, so that the transfer efficiency remains practically constant. The excimer formation and dissociation rate parameters in the pure alkyl benzenes are evaluated.


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