Surface modification of protein nanocontainers and their self-directing character in polymer blends

Tailoring the surfaces of a nanocontainer with polymer brushes that have different affinities to the components of a phase-separating polymer blend should impart self-directing properties to the nanocontainers. Such nanocontainers could then be used to deliver a variety of functional species in tunable amounts and in a site-specific manner to polymer systems. This paper describes the surface modification, subsequent characterization of nanocontainers derived from ferritin, and the effects of surface modification on their self-directing properties in a binary phase-separating homopolymer blend. Wild ferritin was either PEGylated or alkylated by zero-length cross-linking to its surface carboxylate groups that were activated by carbodiimide. Modification was confirmed by ion-exchange chromatography, ζ-potential measurement, and electrospray ionization mass spectrometry. FT-IR spectrometry was used to quantify the extent of PEGylation by ratioing the intensity of the C-O-C asymmetric stretching vibration from the grafted PEG to that of the carbonyl stretching vibration (amide I band) from the protein. Importantly, modified ferritin was soluble in the organic solvent dichloromethane (DCM). Modified ferritin was introduced into a polymer blend of hydrophobic and hydrophilic polymers made up of poly(desaminotyrosyl tyrosine dodecyl ester carbonate) (PDTD) and PEG by solvent casting from solution in the common solvent DCM. Polymer thin films with an average thickness of ∼200 μm were obtained upon evaporation of the solvent. Transmission electron micrographs of microtomed polymer films demonstrated remarkable selectivity of PEGylated ferritin to PEG domains, while alkylated ferritin self-directs to the PDTD matrix.