Aging of poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene)/toluene solutions and subsequent effects on luminescence behavior of cast films.

Morphological effects in luminescence properties of a representative semiconducting polymer, poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV), has recently attracted much attention. Previous studies indicated that short-term heat treatment of solution-cast MEH-PPV films may result in the formation of mesomorphic order that is responsible for the "red" emission around 640 nm, in contrast to the single-chromophore "yellow" emission near 590 nm from the disordered matrix. On the basis of microscopic and spectroscopic evidence for films cast from freshly prepared and aged solutions, here we show that prolonged storage of MEHyellowPPV solutions at room temperature or lower may result in retardation of the thermally induced mesophase formation in the subsequently cast films. According to small-angle neutron scattering and differential scanning calorimetric observations over aged MEH-PPV/toluene solutions, we propose that the suppressed transformation into mesomorphic order is due to further development of nanocrystalline aggregates that serve as physical cross-links among MEH-PPV chains in the solution state upon long-term storage. These solvent-induced nanocrystalline aggregates, however, do not exhibit new spectroscopic features beyond the suppression of "red" emission at 640 nm from the mesomorphic phase.

Triplet-to-singlet exciton formation in poly(p-phenylene-vinylene) light-emitting diodes.

The triplet to singlet exciton formation ratio in a MEH-PPV light-emitting diode is measured by comparing the triplet-induced absorptions with optical and electric excitations at the same singlet exciton density. The ratio is a strong universal decreasing function of the averaged electric field. Using 4 ns for singlet to triplet intersystem crossing time, the ratio is significantly larger than the spin-independent value 3 at intermediate field but is reduced to about 2 for higher field.

Efficient light harvesting by sequential energy transfer across aggregates in polymers of finite conjugational segments with short aliphatic linkages.

Interactions between lumophores have a critical influence on the photophysical properties of conjugated polymers. We synthesized a new series of light-harvesting polymers (poly-DSBs, I-IV) of dialkyloxy- or dialkyl-substituted distyrylbenzene (the substituents being methoxy, 2-ethylhexyloxy, and cyclohexyl) with short aliphatic linkage (methylene or ethylene) and examined the effects of interactions between lumophores and of chemical structures on the absorption, emission, and excitation spectra. The proximity between distyrylbenzene lumophores was shown to be critical to the interactions between lumophores and to the energy-transfer processes. In concentrated solutions and solid films, intermolecular aggregates exist resulting from different extents of interactions between lumophores and are found to involve at least three species: loose, compact, and the most aligned aggregates as observed by photoluminescence and excitation spectroscopies. We also found, for the first time, sequential energy transfer from individual lumophores to the most compact, aligned aggregates via the looser intermolecular aggregates, as observed directly by time-resolved fluorescence spectroscopy. Such a process mimics energy transfer in photosynthesis units and is so efficient such that the fluorescence color can be red-shifted drastically by the presence of comparatively few aggregates and that the light evolved from concentrated solutions and films of poly-DSBs I-IV is entirely or almost the aggregation emission. Although the sequential energy-transfer process in fully conjugated electro-/photoluminescent polymers due to inhomogenity other than distributed conjugation lengths has never been directly observed at room temperature, we suggest that events similar to those observed in poly-DSBs in conjugated polymers could occur but on a much shorter time scale, i.e., a few picoseconds.

Mandibular second molar periodontal status after third molar extraction.

BACKGROUND: Extraction and treatment of third molars have been cited as causing periodontal problems. To evaluate the long-term effects of third molar extraction on the periodontal health of the mandibular second molar, a comparison of the periodontal status was performed around 2 groups of mandibular second molars, with and without third molar extraction. METHODS: A total of 312 sites in 57 adult periodontitis patients were examined and the buccal and lingual locations of the mesial and distal root surfaces around the second molars were recorded. Two-hundred and thirty-two sites were experimental teeth; i.e., third molars had been surgically removed more than 5 years ago, 80 sites served as control molars; i.e., congenitally missing third molars. Clinical periodontal parameters including probing depth, attachment loss, and gingival recession and radiographic intrabony level were measured. The effects of the surgery and the examination (buccal or lingual) locations on the measurements were statistically analyzed. RESULTS: Neither extraction history nor examination location affected the probing depth on mesial surfaces. However, significant effects of the surgical history on the probing depth were observed on the distal surfaces. Similar results of greater attachment loss and radiographic alveolar bone loss were observed only at the distal sites of the experimental group. In addition, the increased radiographic bone loss was only found at the distal sites (adjacent to the surgical location) and not at the mesial sites (distant from the surgical location) on the experimental group. CONCLUSIONS: In this study, greater periodontal breakdown, including probing depth, attachment loss, and radiographic alveolar bone loss, was found at the distal sites, but not at the mesial sites, of the experimental molars where the third molar was surgically extracted compared with the control teeth (no surgery). In the experimental molars, more radiographic bone loss was found at the sites adjacent to the surgical location than at the sites distant to the surgical location. Therefore, we suggest that the surgical removal of the mandibular third molar may lead to a periodontal breakdown on the distal surface of the second molar. Periodontal re-evaluation after the initial healing of third molar extraction is indicated.