Starting from the fourfold ethynyl-substituted chromophore 1,3,6,8-tetraethynylpyrene as core, a series of polyphenylene dendrimers was prepared in high yield by combining divergent and convergent growth methods. The fluorescence quantum yields (Q(f)>0.92) of the encapsulated pyrene chromophore were independent of the size of the polyphenylene shell. Fluorescence quenching studies and temperature-dependent fluorescence spectroscopy were performed to investigate the site isolation of the core. They indicate that a second-generation dendrimer layer is needed to efficiently shield the encapsulated pyrene and prevent aggregate formation. Alkali-metal reduction of the encapsulated pyrene core was carried out to afford the corresponding pyrene radical anions, for which hampered electron transfer to the core was observed with increasing dendrimer generation, which is further proof of the site isolation due to the polyphenylene shell. To improve film formation and solubility of the material, solubilizing alkyl chains were introduced on the periphery of the spherical particles. Furthermore, highly transparent films obtained by a simple drop-casting method showed blue emission mainly from the unaggregated species. The materials presented herein combine high quantum efficiency, good solubility, and improved film-forming properties, which make them possible candidates for several applications in electronic devices.
Photoinduced electron transfer (ET) processes in a donor-acceptor system based on triphenylamine and perylene imide have been studied at the single-molecule (SM) and ensemble levels. The system exists as two isomers, one of which undergoes forward and reverse ET in toluene with decay constants of 3.0 and 2.2x10(9) s(-1), respectively, resulting in the dual emission of quenched and delayed fluorescence while the other isomer remains ET-inactive. The fluorescence of both isomers is heavily quenched in the more polar solvent, diethyl ether, by ET. A broad range of ET dynamics is seen at the SM level in polystryene with the two isomers nonresolvable indicating that the local nanoenvironment of the SMs varies considerably throughout the polymer matrix. Both the electronic coupling and the driving force for ET are shown to influence the ET dynamics. Many fluorescence trajectories of SMs show long periods (tens of milliseconds to seconds) where the count rate is attenuated either partly (a "dim" state) or to the background level (an "off-time"). During these periods, the reduction or interruption of emission is attributed to cycles of rapid charge separation followed by charge recombination to the ground state reducing the fluorescence quantum yield of the SM.
We demonstrate super-resolution imaging of proteins and nucleic acids that were densely labelled with fluorophores using the concept of “click chemistry”.
Methylated β-cyclodextrin was used to complex the hydrophobic monomers n-propyl acrylate (1), n-butyl acrylate (2), n-pentyl acrylate (3), n-hexyl acrylate (4), and cyclohexyl acrylate (5) respectively yielding the corresponding water-soluble host/guest-complexes 1a-5a. The complexes were polymerized in water by free radical mechanism and the initial polymerization rates (v 0) determined. We found that v0 increases as follows: 1a (12.5), 2a (27.5), 3a (44.2), 5a (49.4), 4a (75.8 × 10 -6 mol‚L -1 ‚s -1 ). To investigate the influence of the hydrophobic character of the guest monomers on the reaction rate, the water solubilities of the uncomplexed monomers 1-5 were determined by HPLC measurements. It was generally shown that with increase of water solubility of the free monomers the initial reaction rate (v0) decreases significantly.
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