Supramolecular assembly of block copolypeptides with semiconductor nanocrystals.

We report the analogy between the self-assembly properties of amphiphilic phospholipids and the similar behavior observed for quantum dot (CdSe/CdS)-diblock copolypeptide hybrid systems, and the effect of the self-assembly on secondary structures of the polypeptides. At neutral pH, the diblock copolypeptide, poly(diethyleneglycol-l-lysine)-poly(l-lysine), comprises a positively charged poly-l-lysine (PLL) block and a hydrophilic and uncharged poly(diethyleneglycol-l-lysine) (PEGLL) block. By itself, the copolypeptide is not amphiphilic. However, when the polymers are mixed with water-soluble, negatively charged, citrate-functionalized quantum dots (QDs) in water, shell-like structures or dense aggregates are spontaneously formed. Electrostatic and hydrogen-bonding interactions between the positively charged PLL residues and the negatively charged ligands on the QDs lead to charge neutralization of the PLL block, while the PEGLL block remains hydrophilic. As a result, a pseudo "amphiphilic" molecular unit is formed in which the "hydrophobic" and hydrophilic sections constitute the charge-neutralized PLL residues together with the associating QD and the remaining polypeptide residues that are not neutralized, respectively. The generation of these "amphiphilic" molecular units in turn drives the formation of the QD-polypeptide assemblies. Support for this analogy comes from the observed transition in the shape of the assembly from a shell-like structure to a dense aggregate that is very much analogous to the vesicle-to-micelle transition observed in lipid systems. Furthermore, this shape transition can be explained qualitatively using a concept that is analogous to the surfactant number (N = a(hc)/a(hg)), which has been applied extensively in amphiphilic lipid systems. Specifically, as the ratio of the "hydrophobic" area (a(hc)) to the hydrophilic area (a(hg)) decreases, a shape transition from the shell-like structure to the dense aggregate occurs. In addition, the size of the shell-like structure changes as a function of the dimensions of the "amphiphilic" molecular unit in a manner that is similar to how the size of the lipid vesicle changes with the dimensions of the lipid molecule. Circular dichroism (CD) measurements have shown that the PEGLL-PLL molecule has a well-defined secondary structure (alpha-helical PEGLL block and random coil PLL block) that remains virtually unchanged after reacting with the QDs. This finding is consistent with the hypothesis that it is the electrostatic interaction between the amines on the PLL block and the citrate ligands on the QDs that drives the self-assembly.