Designed dendrimer syntheses by self-assembly of single-site, ssDNA functionalized dendrons

Single site, functionalized, single stranded (ssDNA) dendri-poly(amidoamine) (PAMAM) di-dendrons have been synthesized by covalently conjugating complementary 32 base pair oligonucleotides to single-site, thiol functionalized dendri-PAMAM di-dendrons possessing neutral or anionic surface groups. Combining these complementary (ss-DNA) functionalized PAMAM di-dendrons at appropriate assembly temperatures produced Watson-Crick base paired (dsDNA) cores, surrounded by four PAMAM dendrons. These novel core-shell nanostructures represent a new class of precise monodisperse, linear-dendritic architectural copolymers. Using comparative gel electrophoresis, it was demonstrated that these self-assembled (di-dendron) dendrimers could be hemispherically differentiated as a function of surface chemistry as well as generational size. This new supramacromolecular approach offers a very facile and versatile strategy for the combinatorial design of size, shape, and surface substituents for both homogeneous and differentiated dendritic nanostructures.