RESUMO
The specific optical absorption of an organic semiconductor is critical to the performance of organic optoelectronic devices. For example, higher light-harvesting efficiency can lead to higher photocurrent in solar cells that are limited by sub-optimal electrical transport. Here, we compare over 40 conjugated polymers, and find that many different chemical structures share an apparent maximum in their extinction coefficients. However, a diketopyrrolopyrrole-thienothiophene copolymer shows remarkably high optical absorption at relatively low photon energies. By investigating its backbone structure and conformation with measurements and quantum chemical calculations, we find that the high optical absorption can be explained by the high persistence length of the polymer. Accordingly, we demonstrate high absorption in other polymers with high theoretical persistence length. Visible light harvesting may be enhanced in other conjugated polymers through judicious design of the structure.
RESUMO
Tetraphenylhexaazaanthracene (TPHA), a fluorescent zwitterionic biscyanine with a closed-shell singlet ground state, on treatment with manganese dioxide or phenyliodine bis(trifluoroacetate) (PIFA), undergoes oxidative dimerization to give a near-zero dipole scissor 5,5'-dimer DI-TPHA. Both acene components of the new dimer DI-TPHA maintain their biscyanine closed-shell singlet ground state motifs, as judged by analysis of both single crystal X-ray crystallographic and density functional theory computational studies; however, unlike TPHA, DI-TPHA is only very weakly fluorescent.
RESUMO
The 11-residue peptide fragment from transthyretin (TTR(105-115)) has been investigated using UV resonance Raman spectroscopy. Excitation at 239.5 nm reveals selective enhancement of scattering from two Tyr residues. The titrating behavior of the tyrosines is followed through the change in the Y8a band (1617 cm(-1)) frequency as a function of pH, and a pK(a) = 10.2 +/- 0.2 is obtained. This is compared to the value of 9.1 +/- 0.2 for the pK(a) of aqueous Tyr also obtained in the present study. The pK(a) difference observed here, along with observations in the nu(OH) region, suggest that the two Tyr residues in the peptide probe two distinct microenvironments.