ABSTRACT
A promising approach to influence and control the photophysical properties of conjugated polymers is directing their molecular conformation by templating. We explore here the templating effect of single-stranded DNA oligomers (ssDNAs) on cationic polythiophenes with the goal to uncover the intermolecular interactions that direct the polymer backbone conformation. We have comprehensively characterized the optical behavior and structure of the polythiophenes in conformationally distinct complexes depending on the sequence of nucleic bases and addressed the effect on the ultrafast excited-state relaxation. This, in combination with molecular dynamics simulations, allowed us a detailed atomistic-level understanding of the structure-property correlations. We find that electrostatic and other noncovalent interactions direct the assembly with the polymer, and we identify that optimal templating is achieved with (ideally 10-20) consecutive cytosine bases through numerous π-stacking interactions with the thiophene rings and side groups of the polymer, leading to a rigid assembly with ssDNA, with highly ordered chains and unique optical signatures. Our insights are an important step forward in an effective approach to structural templating and optoelectronic control of conjugated polymers and organic materials in general.
ABSTRACT
Perylene bisimides (PBIs) are dyes known for combining high absorption and emission in the visible region with thermal and photochemical stability. H-bond-directed aggregation driven by free imide groups has been reported to promote the uncommon J-type aggregate formation of PBIs. J-aggregates are highly desired thanks to their bathochromically shifted narrow absorption and fluorescence due to excitonic coupling, together with hyperchromicity and superradiance compared to the monomer. Herein we present the water soluble MEG-PBI showing interesting aggregation in water and in the solid state. Unlike its hydrophobic counterparts, MEG-PBI aggregates in water with increasing temperature, indicating entropy-driven self-assembly. Temperature-dependent Resonance Raman (RR) spectroscopy was employed for the structural characterization of MEG-PBI in aqueous solution versus toluene and in aggregated thin films, employing excitation at different wavelengths to probe the contribution of various chromophores to the supramolecular structure of the aggregate. We find that the perylene core distorts upon aggregation, where the bonds along the perylene long N-N axis lengthen and the ones perpendicular to that shorten, suggesting a head-to-tail arrangement due to H-bonding between neighboring units.
ABSTRACT
We report here the photophysical properties of a water-soluble conjugated polythiophene with cationic side-chains. When dissolved in aqueous buffer solution (PBS, phosphate buffered saline), there is ordering of the polymer chains due to the presence of the salts, in contrast to pure water, where a random-coil conformation is adopted at room temperature. The ordering leads to a pronounced colour change of the solution (the absorption maximum shifts from 400 nm to 525 nm). Combining resonance Raman spectroscopy with density functional theory computations, we show a significant backbone planarization in the ordered phase. Moreover, the ratio of ordered phase to random-coil phase in PBS solution, as well as the extent of intermolecular interactions in the ordered phase, can be tuned by varying the temperature. Femtosecond transient absorption spectroscopy reveals that the excited-state behaviour of the polyelectrolyte is strongly affected by the degree of ordering. While triplet state formation is favoured in the random-coil chains, the ordered chains show a weak yield of polarons, related to interchain interactions. The investigated polyelectrolyte has been previously used as a biological DNA sensor, based on optical transduction when the conformation of the polyelectrolyte changes during assembly with the biomolecule. Therefore, our results, by correlating the photophysical properties of the polyelectrolyte to backbone and intermolecular conformation in a biologically relevant buffer, provide a significant step forward in understanding the mechanism of the biological sensing.
ABSTRACT
Nanometric TiO2 has been reported to be cytotoxic and genotoxic in different in vitro models when activated by UV light. However, a clear picture of the species mediating the observed toxic effects is still missing. Here, a nanometric TiO2 powder has been modified at the surface to completely inhibit its photo-catalytic activity and to inhibit the generation of all reactive species except for singlet oxygen. The prepared powders have been tested for their ability to induce strand breaks in plasmid DNA and for their cytotoxicity and genotoxicity toward human keratinocyte (HaCaT) cells (100-500 µg mL(-1), 15 min UVA/B exposure at 216-36 mJ m(-2) respectively). The data reported herein indicate that the photo-toxicity of TiO2 is mainly triggered by particle-derived singlet oxygen. The data presented herein contribute to the knowledge of structure-activity relationships which are needed for the design of safe nanomaterials.
