Effect of Buffer Anions on Pearl-Necklace Morphology of Tertiary Amine-Containing Binary Heterografted Linear Molecular Bottlebrushes in Acidic Aqueous Buffers.

Molecular bottlebrushes can exhibit a multitude of distinct conformations under different conditions, and precise control of their morphology can facilitate better use of such materials in potential applications. Herein, we report a study on the effect of buffer anions on the pearl-necklace morphology of linear binary heterografted molecular brushes consisting of pH-responsive poly(2--diethylamino)ethyl methacrylate) (PDEAEMA) with a p of 7.40 and thermoresponsive poly(ethoxydi(ethylene glycol) acrylate) (PDEGEA) with a lower critical solution temperature of 9 °C as side chains in various acidic aqueous buffers at 0 °C. The molecular brushes, denotated as BMB, were prepared by a grafting-to approach using copper(I)-catalyzed azide-alkyne cycloaddition reaction. Dynamic light scattering studies showed that the apparent hydrodynamic size of BMB in aqueous buffers with a pH of 6.50 at 1 °C decreased with increasing valency of buffer anions, from acetate anions with a charge of 1-, to phosphate anions carrying charges of 2- and 1- and citrate anions bearing charges of 3- and 2- at pH = 6.50. Atomic force microscopy revealed that BMB exhibited a pearl-necklace morphology from all three aqueous buffers with a pH of 6.50 when spin-cast at 0 °C. Analysis of AFM images showed that the average length of BMB and the number of beads per brush molecule decreased with increasing valency of buffer anions while the size and height of the beads increased. The pearl-necklace morphology of BMB was believed to be the result of microphase separation of the neutral PDEGEA and the charged PDEAEMA side chains along the brush backbone. Multivalent kosmotropic buffer anions formed bridging linkages between protonated tertiary amine moieties and thus "crosslinked" the charged PDEAEMA side chains, resulting in the shrinkage of BMB and enhanced microphase separation of two side chain polymers.