Macromolecules, Vol.49, No.24, 9597-9604, 2016
Characterization of the Long-Range Internal Dynamics of Pyrene-Labeled Macromolecules by Pyrene Excimer Fluorescence
The long-range internal dynamics (LRID) of 74 pyrene-labeled macromolecules (PyLMs) were characterized in four solvents representing a broad range of dielectric constants equal to 2.4 (toluene), 7.6 (tetrahydrofuran, THF), 37.8 (N,N-dimethylformamide, DMF), and 46.7 (dimethyl sulfoxide, DMSO). The LRID of the PyLMs were quantified based on the parameters retrieved from the global model free analysis (MFA) of the time-resolved fluorescence (TRF) decays of the pyrene monomer and excimer. These parameters were combined to yield < k >, the average rate constant of pyrene excimer formation in the PyLMs, and (I-E/I-M)(TRF)(f(free) = 0), the ratio of excimer to monomer fluorescence intensity obtained in the absence of pyrene labels that do not form excirner. (I-E/I-M)(TRF)(f(free) = 0) was found to increase linearly with increasing < k > values over 3 orders of magnitude in the four solvents studied with a. slope that,equaled the average lifetime of the pyrene excimer (TO. The < k > values obtained to build these master lines could be correlated back to the expected LRID of the macromolecules. The lowest < k > values were obtained for the end-labeled linear chains holding the pyrene groups far apart, whereas the branched macromolecules bringing the pyrene labels close to each other yielded the larger < k > values. Furthermore, the fact that these master curves were observed for so many different PyLMs in the four solvents covering such a broad range of solvent polarity suggests that this relationship represents a general physical phenomenon that applies to all PyLMs. Considering the importance of characterizing the LRID of macromolecules in solution, the (I-E/I-M)(TRF)(f(free) = 0) vs < k > plots presented in this report can be viewed as calibration curves against which the LRID of any PyLM can now be compared. Thus, the 3 orders of magnitude range found for these master curves offers the scientific community an impressive analytical opportunity to gauge the LRID of macromolecules in solution.