Aggregation Behavior of
the Template-Removed 5,10,15,20-Tetrakis(4-sulfonatophenyl)porphyrin
Chiral Array Directed by Poly(ethylene glycol)-<i>block</i>-poly(l‑lysine)
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Abstract
Complexation between 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin
(TPPS) and poly(ethylene glycol)-<i>block-</i>poly(l-lysine) (PEG-<i>b</i>-PLL) was performed via electrostatic
interaction. Two kinds of primary arrays of TPPS with different supramolecular
chirality induced by PLL were obtained in the resultant complex by
inverting the mixing procedure of the two components. These arrays
could be displaced by poly(sodium-<i>p</i>-styrenesulfonate)
(PSS) from the chiral PLL template through competitive electrostatic
complexation, and then PSS formed a polyion complex micelle with PEG-<i>b</i>-PLL. The template-removed TPPS arrays preserved their
induced chirality and served as primary subunits for the secondary
aggregation of TPPS. The morphology of the secondary aggregates was
strongly dependent upon the asymmetric primary supramolecular arrangement
of TPPS. The rodlike nanostructure that was ∼200 nm in length
was composed of the primary arrays that showed opposite exciton chirality
between the J- and H-bands. In contrast, the micrometer-sized fibrils
observed were composed of the arrays with the same exciton chirality
at the J- and H-bands