RESUMEN
The model-free (MF) analysis was applied to the fluorescence decays of 32 pyrene-labeled macromolecules to probe their internal dynamics. Depending on whether a pyrene derivative was attached to the chain ends of a linear chain, randomly along a polymer backbone, or at the chain terminals of dendrimers, the MF analysis was applied to probe the dynamics of polymer ring closure, backbone flexibility, or chain terminal mobility, respectively. For those polymeric constructs whose decays could be fitted according to Birks' scheme or the fluorescence blob model (FBM), good agreement was obtained between the rate constant for excimer formation retrieved from the MF analysis
RESUMEN
A novel series of pyrene dendronized porphyrins bearing two and four pyrenyl groups (Py(2)-TMEG1 and Py(4)-TMEG2) were successfully synthesized. First and second generation Fréchet type dendrons (Py(2)-G1OH and Py(4)-G2OH) were prepared from 1-pyrenylbutanol and 3,5-dihydroxybenzyl alcohol. These compounds were further linked to a trimesitylphenylporphyrin containing a butyric acid spacer via an esterification reaction to obtain the desired products. Dendrons and dendronized porphyrins were fully characterized by FTIR and (1)H NMR spectroscopy and their molecular weights were determined by matrix-assisted laser desorption ionization time of flight mass spectrometry. Their optical and photophysical properties were studied by absorption and fluorescence spectroscopies. The formation of dynamic excimers was detected in the pyrene-labeled dendrons, with more excimer being produced in the higher generation dendron. The fluorescence spectra of the pyrene dendronized porphyrins exhibited a significant decrease in the amount of pyrene monomer and excimer emission, jointly with the appearance of a new emission band at 661 nm characteristic of porphyrin emission, an indication that fluorescence resonance energy transfer (FRET) occurred from one of the excited pyrene species to the porphyrin. The FRET efficiency was found to be almost quantitative ranging between 97% and 99% depending on the construct. Model Free analysis of the fluorescence decays acquired with the pyrene monomer, excimer, and porphyrin core established that only residual pyrene excimer formation in the dendrons could occur before FRET from the excited pyrene monomer to the ground-state porphyrin core.
RESUMEN
PE films grafted with poly(methyl acrylate) and labeled with pyrene groups were obtained by irradiation with γ-rays in the presence of acryloyl chloride and further reacting them with 1-pyrenebutanol or 1-pyrenemethylamine. Characterization of the polymer films benefited from the dual use of the pyrene probe as an indicator of, first, polymer chain dynamics by monitoring pyrene excimer formation by fluorescence and, second, polymer morphology by staining the pyrene-rich domains of the films with RuO(4) for scanning electron microscopy (SEM). The grafted polymers labeled with 1-pyrenemethylamine showed much stronger absorbance than those labeled with 1-pyrenebutanol despite having similar pyrene contents. The fluorescence spectra of the grafted polymers labeled with 1-pyrenebutanol exhibited monomer emission, whereas those labeled with 1-pyrenemethylamine exhibited exclusively excimer emission. These dramatic differences could be accounted for by noting that labeling of the grafted poly(acryloyl chloride) with 1-pyrenemethylamine results in cross-linking of the polymer matrix, with an associated enhancement of the concentration of pyrene in the cross-linked domains, which was confirmed by SEM. Formation of discrete domains in the polymer film can induce multiple scattering at the domain boundaries which lengthens the path of light in the film and increases absorption of the light by the tightly packed pyrene-rich domains. Implementation of this effect for fabrication of plastic color filters should generate more efficient filters which should find numerous practical applications.