In Situ Characterization of Binary Mixed Polymer Brush-Grafted Silica Nanoparticles in Aqueous and Organic Solvents by Cryo-Electron Tomography.

We present an in situ cryo-electron microscopy (cryoEM) study of mixed poly(acrylic acid) (PAA)/polystyrene (PS) brush-grafted 67 nm silica nanoparticles in organic and aqueous solvents. These organic-inorganic nanoparticles are predicted to be environmentally responsive and adopt distinct brush layer morphologies in different solvent environments. Although the self-assembled morphology of mixed PAA/PS brush-grafted particles has been studied previously in a dried state, no direct visualization of microphase separation was achieved in the solvent environment.

Environmentally responsive self-assembly of mixed poly(tert-butyl acrylate)-polystyrene brush-grafted silica nanoparticles in selective polymer matrices.

Environmentally responsive self-assembly of nearly symmetric mixed poly(tert-butyl acrylate) (PtBA, 22.2 kDa)/polystyrene (PS, 23.4 kDa) brushes grafted onto 67 nm silica nanoparticles in selective homopolymer matrices [PtBA for the grafted PtBA chains and poly(cyclohexyl methacrylate) (PCHMA) for the grafted PS chains] was investigated using both conventional transmission electron microscopy (TEM) and electron tomography (i.

Truncated Wedge-Shaped Nanostructures Formed from Lateral Microphase Separation of Mixed Homopolymer Brushes Grafted on 67 nm Silica Nanoparticles: Evidence of the Effect of Substrate Curvature.

Mixed poly(-butyl acrylate) (PBA)/polystyrene (PS) brushes with controlled molecular weights and narrow polydispersities were synthesized from asymmetric difunctional initiator (Y-initiator)-functionalized 67 nm silica nanoparticles by sequential surface-initiated atom transfer radical polymerization of BA at 75 °C and nitroxide-mediated radical polymerization of styrene at 120 °C in the presence of a free initiator in each polymerization. The Y-initiator-functionalized nanoparticles were prepared by the immobilization of a triethoxysilane-terminated Y-initiator onto the surface of 67 nm silica particles via an ammonia-catalyzed hydrolysis and condensation process. Transmission electron microscopy studies showed that mixed PBA/PS brushes grafted on 67 nm silica nanoparticles with comparable molecular weights for the two polymers underwent lateral microphase separation after being cast from CHCl and annealed with CHCl vapor, producing distinct truncated wedge-shaped nanostructures.

Temperature- and pH-triggered reversible transfer of doubly responsive hairy particles between water and a hydrophobic ionic liquid.

This article reports on the synthesis of thermo- and pH-sensitive polymer-brush-grafted silica particles ("hairy" particles) and the study of their phase-transfer behavior between water and a hydrophobic ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([EMIM][TFSA]), in response to temperature and pH changes. The hairy particles were made by the surface-initiated atom transfer radical polymerization of methoxytri(ethylene glycol) methacrylate (TEGMMA) and tert-butyl methacrylate with a molar ratio of 100:11 in the presence of a free initiator and the subsequent removal of tert-butyl groups. The cloud points (CPs) of poly(TEGMMA-co-methacrylic acid), obtained after the treatment of the free polymer with trifluoroacetic acid, in both water and [EMIM][TFSA]-saturated water increased with the increase in pH and can be tuned over a wide temperature range.

Spontaneous phase transfer of thermosensitive hairy particles between water and an ionic liquid.

This article describes the temperature-induced phase transfer behavior of a series of thermosensitive polymer brush-grafted particles between water and a hydrophobic ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]). Six samples were made by surface-initiated atom transfer radical polymerization: silica particles grafted with poly(methoxypoly(ethylene glycol) methacrylate) (PPEGMMA) with two different molecular weights, poly(methoxytri(ethylene glycol) methacrylate) (PTEGMMA), poly(methoxydi(ethylene glycol) methacrylate) (PDEGMMA), and two copolymers of PEGMMA and TEGMMA with different compositions (P(PEGMMA-co-TEGMMA)-82 and P(PEGMMA-co-TEGMMA)-74). The cloud points of free PPEGMMA with M(n,SEC) of 23 and 40 kDa, P(PEGMMA-co-TEGMMA)-82, P(PEGMMA-co-TEGMMA)-74, and PTEGMMA in [EMIM][TFSI]-saturated water were 95, 94, 80, 72, and 43 °C, respectively.