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An atom transfer radical polymerization-based sequential “graft-from” approach was developed to synthesize molecular brush-on-brush (MBoB)-based hierarchically branched polymers with readily tunable backbone grafting density, lengths of backbone and primary/secondary side chains, and monomer type. The hierarchically branched structure was visualized, and the stability of the giant MBoB macromolecules was studied by atomic force microscopy. The robust approach enabled the versatile combination of chemical functionality and MBoB structure.

Graphical abstract: Synthesis and visualization of molecular brush-on-brush based hierarchically branched structures

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