ABSTRACT
The understanding of excitonic transitions associated with polymeric aggregates is fundamental, as such transitions have implications on coherence lengths, coherence numbers and inter- and intra-chain binding parameters. In this context, the investigation of efficient solvents and other ways to control polymer aggregate formation is key for their consolidation as materials for new technologies. In this manuscript, we use Poly(3-hexothiophene) (P3HT) as a probe to investigate the significance of amylene (C5H10) and its association with methanol (MeOH) in both pure and C5H10-stabilized chloroform (CHCl3)-based polymeric solutions. Using the intensity ratio between the first and second vibronic transitions of the P3HT H-aggregates formed, values for their exciton bandwidths and interchain interactions are obtained and correlated with the presence of C5H10 and MeOH as agents determining the CHCl3 quality.
ABSTRACT
Solution processing of conjugated polymers into ordered self-assembled precursors has attracted great interest in the past years owing to the ability to manipulate their structural and physical properties. Regioregular poly(3-hexylthiophene) (P3HT) has become the benchmark polymer in this scenario, where ordered lamellar structures significantly improve carrier mobility of the thin films due to increased crystallinity, extended intrachain conjugation, and ordered interchain π-stacking. Here, a new photoinduced approach is presented for the generation of highly ordered P3HT aggregate structures that is amenable to the use of visible light to control the aggregate formation. Strong intra- and interchain interactions in the solution precursors allow for permanent formation of localized and delocalized polarons that are stable for months. Spin-coated thin films are found to preserve, in part, the morphological and physical properties of the aggregated P3HT solution precursors with high degree of crystallinity and short π-stack interchain distances.
ABSTRACT
The present work reports the synthesis, photophysical and photochemical characterization and photodynamic evaluation of zinc, aluminum and metal free-base tetracarboxy-phthalocyanines (ZnPc, AlPc and FbPc, respectively). To evaluate the possible application of phthalocyanines as a potential photosensitizer the photophysical and photochemical characterization were performed using aqueous (phosphate-buffered solution, PBS) and organic (dimethyl sulfoxide, DMSO) solvents. The relative lipophilicity of the compounds was estimated by the octanol-water partition coefficient and the photodynamic activity evaluated through the photooxidation of a protein and photohemolysis. The photooxidation rate constants (k) were obtained and the hemolytic potential was evaluated by the maximum percentage of hemolysis achieved (Hmax) and the time (t50) to reach 50% of the Hmax. Although these phthalocyanines are all hydrophilic and possess very low affinity for membranes (log PO/W=-2.0), they led to significant photooxidation of bovine serum albumin (BSA) and photohemolysis. Our results show that ZnPc was the most efficient photosensitizer, followed by AlPc and FbPc; this order is the same as the order of the triplet and singlet oxygen quantum yields (ZnPc>AlPc>FbPc). Furthermore, together, the triplet, fluorescence and singlet oxygen quantum yields of zinc tetracarboxy-phthalocyanines suggest their potential for use in theranostic applications, which simultaneously combines photodiagnosis and phototherapy.
