Poly(fluorene)-type materials are widely used in polymer-based light emitting devices. In their pristine state, they emit in the deep blue spectral region. During operation there appears, however, an additional emission peak at around 2.3 eV. This observation has usually been attributed to aggregate or excimer formation. Recently, it has been shown that photo- and/or electro-oxidation of poly(fluorene) chains resulting in ketonic defects (i.e., formation of fluorenone groups) can also be held responsible for emission in that spectral region. In this contribution, we apply quantum-chemical techniques to gain a detailed understanding of the optical properties of poly(fluorene)s containing ketonic defects. In particular, we compare model systems for poly(fluorene) with their ketone-containing counterparts, focusing on the influence of excited-state localization effects. The results of the theoretical calculations are confirmed by experimental investigations on statistical copolymers of fluorene and 9-fluorenone.

The low emission band at 2.2–2.3 eV in polyfluorene‐based conjugated materials is studied by various spectroscopic methods on defined copolymers of 9–9′‐difarnesyl‐fluorene with 9‐fluorenone, which can be seen as a model compound for degraded polyfluorenes. Absorption, electroluminescence, and photoluminescence in the film (temperature‐dependent) and solution (room temperature) reveal the optical properties of this low‐energy emission band emerging in polyfluorene‐type polymers upon degradation. All the experimental evidence presented yield direct evidence against excimer or aggregate formation as the primary source of the low‐energy emission band. Instead keto defect sites can be shown to be responsible for the emissive defect.

Using time-resolved and steady-state photoluminescence techniques, fluorene/fluorenone copolymers have been studied to investigate the role of keto defects in degraded polyfluorene. Keto sites can be populated via migration from polyfluorene singlets, thereby quenching the polyfluorene fluorescence, and via direct photon absorption. In the former case, the migration process dominates all thermal and interchain variability in the efficiency of quenching. No annihilation process of fluorenone triplets and no interchain processes such as excimer formation participate in the defect emission itself.

We investigate the oxidative degradation process occurring in ladder-type poly(p-phenylene) (LPPP) by spectroscopic and quantum-chemical techniques. Annealing experiments carried out for two representatives of the class of LPPP's with different side chains relate the change in emissive behavior of the polymer to the presence of ketonic defects on the main chain. The geometry, excitation, and emission energies as well as vibrational modes are calculated for model LPPP oligomers bearing these defects. The optical properties of these molecules are significantly changed compared to the pristine model systems. In the excited-state geometry, ketone-containing oligomers possess emissive excited states in the energy region of the experimentally observed low-energy emission band. The calculated infrared (IR) absorption peaks associated with the defects can also be correlated with the experimental IR spectra.

In this study we investigated whether expanded goat chondrocytes have the capacity to generate cartilaginous tissues with biochemical and biomechanical properties improving with time in culture. Goat chondrocytes were expanded in monolayer with or without combinations of FGF-2, TGF-b1, and PDGFbb, and the postexpansion chondrogenic capacity assessed in pellet cultures. Expanded chondrocytes were also cultured for up to 6 weeks in HYAFF 1 -M nonwoven meshes or Polyactive TM foams, and the resulting cartilaginous tissues were assessed histologically, biochemically, and biomechanically. Supplementation of the expansion medium with FGF-2 increased the proliferation rate of goat chondrocytes and enhanced their postexpansion chondrogenic capacity. FGF-2-expanded chondrocytes seeded in HYAFF 1 -M or Polyactive TM scaffolds formed cartilaginous tissues with wet weight, glycosaminoglycan, and collagen content, increasing from 2 days to 6 weeks culture (up to respectively 2-, 8-, and 41-fold). Equilibrium and dynamic stiffness measured in HYAFF 1 -M-based constructs also increased with time, up to, respectively, 1.3-and 16-fold. This study demonstrates the feasibility to engineer goat cartilaginous tissues at different stages of development by varying culture time, and thus opens the possibility to test the effect of maturation stage of engineered cartilage on the outcome of cartilage repair in orthotopic goat models. ß

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This short communication describes synthesis, optical and electronic properties of novel 9,9-dialkylfluorene-co-fluorenone copolymers which function as model systems for degradation-induced changes in polyfluorene-type semiconducting materials. Only very small fractions of incorporated fluorenone building blocks lead to a dramatic change of the solid state properties (photo-and electroluminescence). The results are discussed in terms of intra-vs. intermolecular excitation energy transfer.