Supported lipid bilayer templated J-aggregate growth: role of stabilizing cation-pi interactions and headgroup...

Controlling the self-assembly of molecules into specific structural motifs has important implications for the design of materials with specific optical properties. We report here the results of a correlated confocal fluorescence-atomic force microscopy (AFM) study of pseudoisocyanine iodide (PIC) self-assembly on supported lipid bilayers. Through judicious selection of bilayer headgroup packing and chemistry, two types of PIC J-aggregates, distinguishable by their absorbance spectra, and both exhibiting strong resonant fluorescence and bathochromic shifts in absorbance relative to the monomer, were isolated. Remarkably, selective templating can be achieved using different zwitterionic headgroups, producing J-aggregates that display a larger bathochromic shift than their solution counterparts. Our correlated confocal-AFM studies coupled with FT-IR spectroscopy suggested that zwitterionic phospholipids mediate J-aggregate formation through specific cation-pi interactions between PIC and the lipid headgroups with the PIC molecules oriented largely perpendicular to the bilayer normal. The existence of the two isoforms further suggests that bilayer headgroup packing plays a key role in controlling interchromophore organization and subsequent aggregate nucleation and growth.