The dependence of several aspects of the fluorescence from 9-anthryl groups, covalently attached by tethers of differing lengths to interior sites of five polyolefinic films whose crystallinities range from 0 to 74%, has been explored between 40 and 400 K. The data are employed to determine microscopically the onsets of various relaxation processes of the polymers, the sensitivity of the probes to changes in their local morphologies, and the distribution of the groups between amorphous and interfacial sites. The results are compared with those from noncovalently attached (doped) 9-methylanthracene molecules. Specifically, the relationship between the lengths of tethers for the 9-anthryl groups, as well as the chemical method by which each tether is attached to the polymer chains, and the ability of the fluorescence from the lumophores to detect the onsets of host relaxation processes are explored. The two attachment methods lead to different distributions of lumophores in the amorphous and interfacial regions of the polymers. Furthermore, very short (one atom; methylene) and very long (12 atoms) tethers allow the 9-anthryl groups to sense changes in the local environments more acutely than a tether of intermediate length (three atoms). The advantages of covalent attachment for this sort of study (specifically, the inability of the probe to diffuse within a film from site-to-site with time) and the limitations of the utility of the data are discussed.

Static and dynamic fluorescence of pyrene has been used to study the polarity of microenvironments of ethylene-co-(vinyl acetate) copolymers of varying compositions. The polarity of these copolymers, defined by the Py-scale, has been compared with low-density polyethylene and poly(vinyl acetate). Linear correlations between vinyl acetate content and either the vibronic ratio, I/III, of the pyrene fluorescence spectra or the fluorescence decay constants, τF, have been obtained. We have also studied the photophysical properties of pyrene sorbed on the polymer surface by vapor deposition or incorporated within the polymer by swelling with a solvent. The photophysical parameters determined by both experiments are virtually the same, demonstrating that pyrene senses the same type of environment throughout the polymer film. Furthermore, in each of the copolymers, the probes experience an average polarity rather than one from domains enriched in either ethylene or vinyl acetate.

The adsorption of Congo red and tinopal CBS dyes on cellulose fibers was investigated using electronic absorption and fluorescence spectroscopies. Hydrogen bonds appear to be relevant for the dye-fiber interactions as indicated by the solvatochromism of Congo red in water, methanol, and dimethyl sulfoxide solutions, and when adsorbed on cellulose fibers. We also demonstrate that electrostatic interactions play an important role in the dye-medium interaction, through the analysis of absorption spectra of Congo red and fluorescence spectra of tinopal in aqueous solutions containing salt and in layer-by-layer nanostructured films with poly(allylamine hydrochloride). For instance, dye adsorption was enhanced when salt was added to the dipping solution, which was explained by the synergistic effect between the conformational changes of the cellulose and changes in the solvation layer around the cellulose chains and around dye molecules. On the basis of the fluorescence results for tinopal CBS, we inferred that dye aggregation is not relevant for adsorption on the fibers. In addition, fluorescence spectroscopy is proven very sensitive for studying the organization of dye molecules in layer-by-layer films, particularly those undergoing irreversible structural changes.

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