Biopolymers such as DNA store information in their chains using controlled sequences of monomers. Here we describe a non-natural information-containing macromolecule that can store and retrieve digital information. Monodisperse sequence-encoded poly(alkoxyamine amide)s were synthesized using an iterative strategy employing two chemoselective steps: the reaction of a primary amine with an acid anhydride and the radical coupling of a carbon-centred radical with a nitroxide. A binary code was implemented in the polymer chains using three monomers: one nitroxide spacer and two interchangeable anhydrides defined as 0-bit and 1-bit. This methodology allows encryption of any desired sequence in the chains. Moreover, the formed sequences are easy to decode using tandem mass spectrometry. Indeed, these polymers follow predictable fragmentation pathways that can be easily deciphered. Moreover, poly(alkoxyamine amide)s are thermolabile. Thus, the digital information encrypted in the chains can be erased by heating the polymers in the solid state or in solution.

Responsive polymeric brushes of poly(methacrylic acid) (PMAA) were grafted from silicon surfaces using controlled surface-initiated atom-transfer radical polymerization (SI-ATRP). The growth kinetics of PMAA was investigated with respect to the composition of the ATRP medium by grafting the polymer in mixtures of water and methanol with different ratios. The dissociation behavior of the polymer layers was characterized by FTIR titration after incubating the polymer-grafted substrates in PBS buffer solutions with different pH values. PMAA layers show a strong pH-dependent behavior with an effective pK(a) of the bulk polymer brush of 6.5 ± 0.2, which is independent of the polymer brush thickness and methanol content of the ATRP grafting medium. The pH-induced swelling and collapse of the grafted polymer layers were quantified in real time by in situ ellipsometry in liquid environment. Switching between polymer conformations at pH values of 4 and 8 is rapid and reversible, and it is characterized by swelling factors (maximum thickness/minimum thickness) that increase with decreasing the methanol content of the SI-ATRP medium.

Well-defined cleavable or non-cleavable soluble polystyrene supports were prepared by atom transfer radical polymerization and utilized for the iterative synthesis of functional hexapeptides. This approach allowed rapid and efficient liquid phase synthesis of peptide-polymer conjugates.

Polymer brushes grafted from surfaces using controlled polymerization techniques, most notably surface-initiated atom-transfer radical polymerization (SI-ATRP), provide robust and reproducible platforms with precise control of surface properties. These platforms are especially useful in biologically oriented applications involving the confinement of membrane proteins onto solid supports, including screening of pharmaceuticals and biosensing. Here we investigate a tunable zwitterion-based polymeric interface that can guide the assembly of neutral lipid membranes with high mechanical stability and reproducibility on various synthetic materials. By controlling the polymer architecture using ATRP, we show that phospholipid membranes can be made to self-assemble on thin layers of charge-balanced poly(sulfobetaine methacrylate) from fusion of DOPC vesicles under physiological conditions. The self-assembly kinetics and functionality of the polymer-supported lipid membranes are investigated using various surface sensitive techniques, including surface plasmon resonance, fluorescence microscopy, and atomic force microscopy. The growth of zwitterionic polymer layers with controlled length and grafting density allows for modulation of the adhesion of the lipid bilayers to surfaces, thus offering unique advantages for the design and synthesis of bioactive surfaces