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  • 1
    ISSN: 1573-4994
    Keywords: DANSyl-labeled copolymers ; swelling volume ; time-resolved fluorescence ; solvent relaxation ; rotational depolarization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract The fluorescent probe dimethylaminonaphthylsulfonamide is covalently bound to the ends of the pol(ethylene glycol) chains of the swellable block copolymers poly(ethylene glycol)–polystyrene (PEG-PS) and poly(ethylene glycol)–poly(ethylene imine) (PEG-PEI) to investigate the molecular mobility inside the polymers, swollen by different liquids. Steady-state and time-resolved studies of the Stokes shift between absorption and fluorescence spectra reveal that the probe is solvated by both the polymer matrix and the liquid phase. The extent of solvation by the liquid and the mobility of the microenvironment of the probe depend on both the swelling volume of the polymer and the solubility of the probe in this liquid. Steady-state and time-resolved fluorescence depolarisation measurements show that the polymer matrix forms a very rigid solvent cage, which almost completely immobilizes the probe. Upon solvation of the probe by the liquid, the mobility of the probe increases. In PEG-PEI swollen by polar solvents, the mobilities of the probe itself and of its microenvironment, although not reaching the values observed in homogeneous solution, are significantly higher than in PEG-PS, due to the hydrophilic nature of the polymeric backbone in PEG-PEI.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1573-4994
    Keywords: Thin organic films ; vapor-deposited oligothiophenes ; quantum yields
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract The fluorescence quantum yields of vapor-deposited (VD) films of α-oligothiophenes,nT, with ring numbers ofn=3–8 and layer thicknesses ofd=3–50 nm were determined at room temperature andT=77 K and compared to the yields of dilute solutions and small (5T)x clusters. The yields of highly oriented ultrathin films are of the order of ΦF=5*10−5-1*10−4. The yields increase strongly with the layer thickness and also upon cooling, but do not reach the values in dilute solution. The main nonradiative deactivation step S1 → T1 in solution was quantified by1O2 production, the yields of which systematically decrease withn from ΦF (3T) to 0.36 (6T), in contrast to the fluorescence yields, which increase from ΦF=0.01 (2T) to 0.40 (6T). In films or clusters the S1 → T1 deactivation step must be a very unimportant side reaction: neither1O2 nor any signal of triplet-triplet absorption could be positively identified.
    Type of Medium: Electronic Resource
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