Influence of magnetic micelles on assembly and deposition of porphyrin J-aggregates

Clusters of superparamagnetic iron oxide nanoparticles (SPIONs) have been incorporated into the hydrophobic core of polyethylene glycol (PEG)-modified phospholipid micelles. Two different PEG-phospholipids have been selected to guarantee water solubility and provide an external corona, bearing neutral (SPIONs@PEG-micelles) or positively charged amino groups (SPIONs@NH2-PEG-micelles). Under acidic conditions and with specific mixing protocols (porphyrin first, PF, or porphyrin last, PL), the water-soluble 5,10,15,20-tetrakis-(4- sulfonatophenyl)-porphyrin (TPPS) forms chiral J-aggregates, and in the presence of the two different types of magnetic micelles, an increase of the aggregation rates has been generally observed. In the case of the neutral SPIONs@PEG-micelles, PL protocol affords a stable nanosystem, whereas PF protocol is effective with the charged SPIONs@NH2-PEG-micelles. In both cases, chiral J-aggregates embedded into the magnetic micelles (TPPS@SPIONs@micelles) have been characterized in solution through UV/vis absorption and circular/linear dichroism. An external magnetic field allows depositing films of the TPPS@SPIONs@micelles that retain their chiroptical properties and exhibit a high degree of alignment, which is also confirmed by atomic force microscopy.