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Grafting of functional methacrylate polymer brushes by photoinduced SET-LRP
Photoinduced surface-initiated single electron transfer living radical polymerization (SET-LRP) is a versatile technique for the preparation of polymer brushes. The vast diversity of compatible functional groups, together with a high end-group fidelity that enables precise control of the architecture, makes this approach an effective tool for tuning the properties of surfaces. We report the application of photoinduced SET-LRP for the surface-initiated grafting of polymer brushes from a wide range of methacrylate monomers for the first time. The living character of the process was demonstrated by the linear evolution of the polymer brush thickness in time, the ability to reinitiate the polymerization for the preparation of well-defined block copolymers, and also by X-ray photoelectron spectroscopy depth profiling. The surface patterning with these brushes could be achieved simply by restricting the irradiated area. The ability of poly(methacrylate) brushes prepared in this way to prevent non-specific protein adsorption is also demonstrated, indicating the suitability of this procedure for advanced applications.
Screening Libraries of Amphiphilic Janus Dendrimers Based on Natural Phenolic Acids to Discover Monodisperse Unilamellar Dendrimersomes
Natural, including plant, and synthetic phenolic acids are employed as building blocks for the synthesis of constitutional isomeric libraries of self-assembling dendrons and dendrimers that are the simplest examples of programmed synthetic macromolecules. Amphiphilic Janus dendrimers are synthesized from a diversity of building blocks including natural phenolic acids. They self-assemble in water or buffer into vesicular dendrimersomes employed as biological membrane mimics, hybrid and synthetic cells. These dendrimersomes are predominantly uni- or multilamellar vesicles with size and polydispersity that is predicted by their primary structure. However, in numerous cases, unilamellar dendrimersomes completely free of multilamellar assemblies are desirable. Here, we report the synthesis and structural analysis of a library containing 13 amphiphilic Janus dendrimers containing linear and branched alkyl chains on their hydrophobic part. They were prepared by an optimized iterative modular synthesis starting from natural phenolic acids. Monodisperse dendrimersomes were prepared by injection and giant polydisperse by hydration. Both were structurally characterized to select the molecular design principles that provide unilamellar dendrimersomes in higher yields and shorter reaction times than under previously used reaction conditions. These dendrimersomes are expected to provide important tools for synthetic cell biology, encapsulation, and delivery.