Poly , phosphorescence excitation

The fluorescence and phosphorescence excitation and emission spectra of commercial polypropylene and poly(4-methylpent-l-ene) are examined using a fully compensated spectrofluorimeter. The excitation spectra of the polymers are compared with the absorption spectra of model chromo-phores of those believed to be present in the polymers. The fluorescence emission is associated primarily with the presence of enone and the phosphorescence is associated with dienone impurity chromophoric units. Bromination of cold hexane extracts of the polymers reduces significantly the intensity of the fluorescence confirming the presence of ethylenic unsaturation. The behavior of the luminescent enone and dienone groups during irradiation under sunlight-simulated conditions is examined also. Possible mechanisms for the participation of these chromophoric units in the photooxidation of the polymers are discussed. 

Polymer Luminescence Spectra. Figure 1 shows typical fluorescence and phosphorescence excitation and emission spectra obtained from commercial polypropylene film (or powder). Poly(4-methylpent-l-ene) exhibits similar spectra to those of polypropylene. The excitation spectrum for the fluorescence has two distinct maxima at 230 and 285 nm while that of the phosphorescence has only one distinct maximum at 270 nm with rather weak and diffuse structure above 300 nm. It is clear from these results that the fluorescent and phosphorescent chromophoric species cannot be the same. This, of course, does not rule out the fact that both may arise from carbonyl emitting species, as will be shown later, since these chromophoric groups when linked to ethylenic unsaturation can have quite distinct absorption (14) and emission spectra (15,16,17). 

Figure 3. Comparison of the phosphorescence excitation spectra of polypropylene (----) and poly(4-methylpent-l-ene) (---) with the absorption...

FIGURE 33. Phosphorescence excitation and emission spectra of photo- (dotted) and thermally (solid oxidized poly(butadiene) [after figure in Eur. Polym. J., 10, 593 (1974)]. 

Fluorescence and phosphorescence spectra of poly(propynoic acid)(FPA), polyphenylene (PP), and DPAcN show that the difference of energies between the lower excited singlet and triplet states, as observed in the case of PP (583 nm) and DPAcN (528 nm), is considerably greater than that of poly(propynoic acid) (270—300 nm) which besides transitions may undergo rr - transitions. PCSs showing only... 

Thymidine phosphate and cytidine phosphate do not phosphoresce in a rigid ethylene glycol-water glass at 77°K109 when directly excited, but thymidine which has lost its proton at Nx does have a triplet which phosphoresces with a decay time of 0.50 sec at high pH uridine also fluoresces with a similar decay time. The quenching of purine fluorescence and appearance of T" fluorescence in UV-irradiated DNA and poly dAT (as well as U" fluorescence in poly rAU) was attributed by Rahn et al.109 to proton transfer from thymine to adenine. This quenches adenine fluorescence and enhances thymine fluorescence. 

A review of chemiluminescent and bioluminescent methods in analytical chemistry has been given by Kricka and Thorpe. A two-phase flow cell for chemiluminescence and bioluminescencc has been designed by Mullin and Seitz. The chemiluminescence mechanisms of cyclic hydrazides, such as luminol, have been extensively analysed. " Fluorescence quantum yields of some phenyl and phenylethynyl aromatic compounds in peroxylate systems have been determined in benzene. Excited triplet states from dismutation of geminate alkoxyl radical pairs are involved in chemiluminescence from hyponitrite esters. Ruorophor-labelled compounds can be determined by a method based on peroxyoxalate-induced chemiluminescence. Fluorescence and phosphorescence spectra of firefly have been used to identify the multiplicity of the emitting species. " The chemiluminescence and e.s.r. of plasma-irradiated saccharides and the relationship between lyoluminescence and radical reaction rate constants have also been investigated. Electroluminescence from poly(vinylcarbazole) films has been reported in a series of four... 

The PL spectrum of a thin film of poly(3,6-dibenzosilole) 31 at 77 K exhibited a 0-0 transition at 3.5 eV and a second maximum at 3.3 eV (excitation at 4.4 eV) [41]. The phosphorescence emission spectrum at 77K consists of a broad band exhibiting vibronic structure (excitation at 3.9 eV). The polymer triplet energy level was taken to be the onset of triplet emission at 2.55 eV. This is considerably higher than the triplet energy of commonly used polyfluorenes (2.1 eV) [10,46] making it a host for phosphorescent emitters without the risk of energy back-transfer onto the polymer. 

Because of its spin-forbidden nature, the decay rate of the first excited triplet state is extremely low, and very difficult to quantify accurately. What can be measured is the phosphorescence lifetime. Typical long time decays for a poly(bi-spirofluorene) (PSBF) are shown in Fig. 6. 

The phosphorescence of BP (0.17 ) in poly(vinyl alcohol) (PVA) film (250 micron thickness) excited by a 10-ns nitrogen laser pulse at 337 nm decays exponentially for T < T (-100°C) or T > T (85°C), but deviates from single exponential for T < T < T. The eviation was attributed to the diffusion-controlled hydrogen abstractlon reaction between benzophenone triplet and the PVA matrix (33). 

With a glassy solution of poly-1-vinylnaphthalene, the delayed emission spectrum has been shown to consist of an emission having a mean lifetime of approximately 80 ms at the normal fluorescence wavelength, in addition to the phosphorescence having a mean lifetime of about 2 s [159]. The delayed fluorescence did not appear in the spectrum of 1-ethylnaphthalene. With the polymer it was found to be inhibited by piperylene, a well-known triplet quencher. These results have been explained by mutual annihilation of two excited triplet states produced by the absorption of two photons by the same polymer molecule. They are considered as strong evidence for migration of the excited triplet state in poly-1-vinylnaphthalene. In polyacenaphthalene, however, which is chemically very similar to poly-1-vinylnaphthalene (see p. 409), no delayed fluorescence could be detected in the same experimental conditions [155]. 

A dual-analyte fiber optic biosensor for O2 and glucose was developed by Li and Walt [22] based on O2 quenching of a phosphorescent ruthenium dye. Excitation was at X = 480 nm, with fluorescent emission captured by a CCD camera. A relatively large (350 (U,m diameter) imaging fiber with 6000 elements was modified by attaching two separate drops of ruthenium dye encapsulated in poly(hydroxyethyl methacrylate) polymer (HEMA). The ruthenium dye allowed measurements of O2 in both encapsulated drops, which were approximately 50 ixm in diameter. A two-site Stern-Volmer quenching model (equation (4.32) with n — 2) was used to determine O2 concentration from measurements of fluorescence intensity. One of the drops had the enzyme glucose oxidase (EC... 

Poly(butadiene) is transparent to sunlight unless thermally oxidized, when it becomes photo-unstable. It has been established that, upon thermal oxidation, the polymer becomes phosphorescent at low temperatures, with emission and excitation spectra (Figure 33) typical of an a3-unsaturated carbonyl (128). If the sample is photolrradlated the phosphorescence spectrum changes into that typical of a saturated carbonyl. Clearly a complete photooxlda-tlon mechanism must Incorporate reactions to explain such observations, but given the very great sensitivity of the Ixmlnescence... 

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