Comblike Polymers with Topologically Different Side Chains for Surface Modification: Assembly Process and Interfacial Physicochemical Properties

The effects of side-chain topology within comblike polymers (CLPs) are revealed when these are assembled on inorganic surfaces to yield dense brush interfaces. CLPs featuring cyclic poly(2-alkyl-2-oxazoline) (PAOXA) side chains and a surface-interacting backbone are less sterically hindered with respect to their linear graft-bearing analogues, show slower adsorption kinetics, and generate denser assemblies on TiO 2 surfaces. Cyclic PAOXA brush interfaces generated from the CLP assembly showed a molecularly smooth and compact nanomorphology, which provides extraordinary lubrication properties to the films when these are sheared against a bare inorganic surface as well as an identical polymer layer, and quantitatively prevent surface contamination within serum-rich media. Topology effects by cyclic segments within highly branched copolymer architectures introduce a new class of surface modifiers, which are broadly applicable in the designing and modification of a variety of materials.