CORALs (CoOrdinated Responsive Arrays of surface-Linked islands) represent a novel approach in the field of responsive surfaces. Polymer CORALs are composed of polymer chains covalently grafted to a solid substrate in a regular manner: islands of densely grafted chains homogeneously separated by a distance on the order of a chain length. Each island of the array is capable of conformational switching in a sharp and coordinated manner. In relaxed state upon exposure to a good solvent CORALs isolate substrate surface from the environment (gas or liquid). In a weak solvent, they adopt a compact conformation thus exposing the surface. This unique behavior distinguishes polymer CORALs from homogeneous polymer brushes and low-density adsorbed/grafted polymer coatings. Thus, polymer CORALs may find applications for responsive heterogeneous catalysts, electrodes, and adsorbents. The control of the switch parameters may be conveniently tuned by the chemical composition of the substrate surface and the parameters (state) of the polymer. We demonstrate it both in the experiment and by the means of course grain molecular simulations. We show that proper chemical modification of the substrate surface significantly shifts the switching conditions, e.g. polarity of the binary solvent. A similar effect has modification of the grafted polymer. In particular, transesterification of poly(tert-butyl methacrylate) with N,N-dimethylaminoethanol results in poly(2-(N,N-dimethylamino)ethylmethacrylate) (PDMAEMA) CORALs. Such CORALs demonstrate conformational response to both temperature and pH

Surface chemistry for modification and tuning of polymer CORALS

2019 Fall National Meeting

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