Polyhedral Oligosilsesquioxane (POSS) Nanoparticle Localization in Ordered Structures Formed by Solvated Block Copolymers

Abstract

The coassembly of polyhedral oligosilsesquioxanes (POSS) of two different surface chemistries is considered, one hydrophilic, poly(ethylene oxide) (PEO), and the other hydrophobic, isobutyl (iB), in cylindrical structures formed by hydrated poly(ethylene oxide)‐poly(propylene oxide)‐poly(ethylene oxide) block copolymer, Pluronic P105 (EO37PO56EO37). Incorporation of PEO‐POSS by replacing an equal mass of water results in an increase in the lattice parameter (d), which is attributed to an increase in the degree of block segregation. In the case of adding PEO‐POSS at a fixed Pluronic P105/water ratio, d ~ φpolymer‐0.7, which suggests that PEO‐POSS particles are located inside the hydrated PEO domains. Incorporation of iB‐POSS in the water‐in‐xylene cylindrical structure causes an order‐to‐order phase transition to a bicontinuous cubic structure, which suggests that iB‐POSS decreases the degree of block segregation by locating at the PEO‐PPO interfacial regions. The nanoparticle versus molecule nature of POSS is discussed by comparing POSS effects to those of 10.6 nm diameter deprotonated silica nanoparticles and of glycerol or glucose.

Nanoparticles in ionic liquids: interactions and organization

“…Structure formation and nanoparticle localization in nanoparticle-LLC composites in molecular solvents, 192,208,209 and LLC structures formed in ionic liquids have been studied. However, ionic liquid-based nanoparticle-LLC composites are much less studied compared with those in regular solvents.…”

Block copolymer–nanoparticle composites: Structure, functional properties, and processing

“…The increase in lattice parameter can be attributed to the swelling of the polymeric domain by NPs [75,154]. For example, the incorporation of deprotonated silica nanoparticles in cylindrical A c c e p t e d M a n u s c r i p t 20 structure formed by hydrated PEO-PPO-PEO BCP increased the lattice parameter at a fixed BCP/water ratio (see Fig.…”

Influence of Substitutional Groups on the Ordering and Crystallization of Amphiphilic Silsesquioxanes at the Air–Water Interface

“…10 The tailored physicochemical properties of the POSS molecules allow them to be used in grafting, blending, and copolymerizing to alter the mechanical strength, thermal stability, glass transition temperature, or crystallization process. 11,12 An exhaustive study of self-assembly of hybrid-polymers utilizing POSS core framework can be found in the review article by Zhang et al 13 Artificially prepared biocompatible advanced materials employ the POSS framework due to their nanosize and robust chemical framework to synthesize bioengineered tissue materials, biocomposites, luminophores, and optical sensors. 14,15 POSS nanocages have been utilized to fabricate photosensitive molecular switches, which demonstrated a unique reversible transformation between cubic lattice and helical superstructures.…”