Inside Block Copolymer Micelles-Tracing Interfacial Influences on Crosslinking Efficiency in Nanoscale Confined Spaces.

Recently, several studies have demonstrated the excellent capabilities of tip-enhanced Raman spectroscopyfor in-depth investigations of structural properties of matter with unprecedented resolution and chemical specificity. These capabilities are utilized here to study the internal structure of core-crosslinked micelles, which are formed by self-assembly of the diblock terpolymer poly(ethylene oxide)-block-poly(furfuryl glycidylether-co-tert-butylglycidyl ether). Supplementing force-volume atomic force microscopy experiments address additionally the nanomechanical properties. Particularly, TERS enables investigating the underlying principles influencing the homogeneity and efficiency of the Diels-Alder core-crosslinking process in the confined hydrophobic core. While the central core region is homogenously crosslinked, a breakdown of the crosslinking reaction is observed in the core-corona interfacial region. The results corroborate that a strong crosslinking efficiency is directly correlated to the formation of a mixed zone of the glycidyl ether and PEO corona blocks reaching ≈5 nm into the core region. Concomitantly a strong exclusion of the encapsulated bismaleimide crosslinker from the interfacial region is observed. It is conceivable that a changed structure, chemical composition and altered nanomechanical properties of this interfacial region may also influence the crosslinking efficiency across the entire core region by a modification of the solubility of the crosslinker in the interfacial core-corona region.