The effect of γ-cyclodextrin addition in the self-assembly behavior of pyrene labeled poly(acrylic) acid with different chain sizes

The interaction between poly(acrylic acid) polymers (PAA) of low- (2000 g/mol) and high- (450,000 g/mol) molecular weight (M-w) hydrophobically modified with pyrene (PAAMePy) and beta- and gamma-cyclodextrins (beta-CD, gamma-CD) was investigated with fluorescent techniques. The interaction with P-CD promotes little variation in the spectral and photophysical behavior of the polymer, whereas significant changes are observed upon addition of gamma-CD. The degree of inclusion (between the pyrene groups of the polymer and the cyclodextrins) is followed through the observation of the changes in the absorption, excitation (collected in the monomer and excimer emission regions) and emission (I-E/I-M ratio) spectra and from time-resolved data. Within the studied range of gamma-CD concentration, the fluorescence decays of the long chain (high Mw) PAAMePy polymers were found tri-exponential in the monomer and excimer emission regions in agreement with previous studies. In the case of the low M-w PAAMePy polymers, tri-exponential decays were observed at the monomer and excimer emission wavelengths. However, when a gamma-CD concentration of 0.01 and 0.03 M is reached for, respectively, the low- and high-labeled pyrene short chain (low M-w) polymers, the fluorescence decays in the excimer region become biexponential (two excimers) with no rising component, thus showing that all pyrene groups are encapsulated (and preassociated) into the gamma-CD cavity. In the case of the high M-w polymers, the addition of gamma-CD has been found to change the level of polymer interaction from pure intramolecular (water in the absence of cyclodextrin) to a coexistence of intrawith intermolecular interactions. (C) 2008 Wiley Periodicals, Inc.