Adsorption of polyelectrolytes onto the oppositely charged surface of tubular J-aggregates of a cyanine dye

Abstract

The adsorption of three different polycations at the negatively charged surface of tubular J-aggregates of the amphiphilic cyanine dye 3,3'-bis(2-sulfopropyl)-5,5',6,6'-tetrachloro-1,1'-dioctylbenzimidacarbocyanine (C8S3) is investigated by means of cryogenic electron microscopy and optical absorption spectroscopy. All three polycations could be adsorbed at the aggregates without flocculation or precipitation when added in molar amounts of monomers sufficiently smaller than of the dye molecules. Preferably the aggregates are either coated by the polycations in total or left completely uncoated. For the coated aggregates, the adsorption leads to charge reversal of the aggregate surface as supported by zeta-potential measurements. The morphology of the coating differs significantly for the three polycations: The branched polycation polyethlyenimine (PEI) attaches to the tubular aggregate by hit-and-stick adsorption of the coiled state in solution forming irregular clot-like coatings; the flexible and weakly cationic poly(allylamine hydrochloride) (PAH) forms a more homogeneous coating but destroys the integrity of the dye aggregate; the more hydrophobic and strong polycation poly(diallyldimethylammonium chloride) (PDADMAC) forms a thin and homogeneous layer, supposedly by wrapping around the tubular aggregate. For the latter, growth of a second dye double layer of the aggregates seems to grow. The different morphologies of the coatings are rather due to the details of the chemical structure of the polycations than due to physical parameters. The possible adsorption of polyelectrolytes at these amphiphilic tubular structures, stabilized by non-covalent bonds only, is far from obvious but demonstrates an applicable route to the build-up of more complex nanostructures by means of a self-assembly process.