title: In Situ Characterization of Binary Mixed Polymer Brush-Grafted Silica Nanoparticles in Aqueous and Organic Solvents by Cryo-Electron Tomography.
abstract: 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. CryoEM allows the sample to be imaged in situ, that is, in a frozen solvated state, at the resolution of a transmission electron microscope. Cryo-electron tomograms (cryoET) were generated for mixed PAA/PS brush-grafted nanoparticles in both N,N-dimethylformamide (DMF, a nonselective good solvent) and water (a selective solvent for PAA). Different nanostructures for the mixed brushes were observed in these two solvents. Overall, the brush layer is more compact in water, with a thickness of 18 nm, as compared with an extended layer of 27 nm in DMF. In DMF, mixed PAA/PS brushes are observed to form laterally separated microdomains with a ripple wavelength of 13.8 nm. Because of its lower grafting density than that of PAA, PS domains form more or less cylindrical or truncated cone-shaped domains in the PAA matrix. In water, PAA chains are found to form a more complete shell around the nanoparticle to maximize their interaction with water, whereas PS chains collapse into the core of surface-tethered micelles near the silica core. The cryoET results presented here confirm the predicted environmentally responsive nature of PAA/PS mixed brush-grafted nanoparticles. This experimental approach may be useful for the design of future mixed brush-grafted nanoparticles for nano- and biotechnology applications.
authors.affiliation: †Department of Pharmacology and Cleveland Center for Membrane and Structural Biology, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, Ohio 44106-4965, United States.
authors.forename: Tara L
authors.initials: TL
authors.lastname: Fox
authors.affiliation: ‡Department of Macromolecular Science and Engineering, Case Western Reserve University, 2100 Adelbert Road, Cleveland, Ohio 44106-7202, United States.
authors.forename: Saide
authors.initials: S
authors.lastname: Tang
authors.affiliation: §Department of Chemistry, University of Tennessee, 1420 Circle Drive, Knoxville, Tennessee 37996, United States.
authors.forename: Jonathan M
authors.initials: JM
authors.lastname: Horton
authors.affiliation: †Department of Pharmacology and Cleveland Center for Membrane and Structural Biology, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, Ohio 44106-4965, United States.
authors.forename: Heather A
authors.initials: HA
authors.lastname: Holdaway
authors.affiliation: §Department of Chemistry, University of Tennessee, 1420 Circle Drive, Knoxville, Tennessee 37996, United States.
authors.forename: Bin
authors.initials: B
authors.lastname: Zhao
authors.affiliation: ‡Department of Macromolecular Science and Engineering, Case Western Reserve University, 2100 Adelbert Road, Cleveland, Ohio 44106-7202, United States.
authors.forename: Lei
authors.initials: L
authors.lastname: Zhu
authors.affiliation: †Department of Pharmacology and Cleveland Center for Membrane and Structural Biology, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, Ohio 44106-4965, United States.
authors.forename: Phoebe L
authors.initials: PL
authors.lastname: Stewart
mesh_terms: D000180:Acrylic Resins / Q000737:chemistry*; D020285:Cryoelectron Microscopy; D004126:Dimethylformamide / Q000737:chemistry*; D053758:Nanoparticles / Q000737:chemistry*; D010316:Particle Size; D011137:Polystyrenes / Q000737:chemistry*; D012822:Silicon Dioxide / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry; D013499:Surface Properties; D014867:Water / Q000737:chemistry
chemical_list: D000180:Acrylic Resins; D011137:Polystyrenes; D012997:Solvents; D014867:Water; C006903:carbopol 940; D012822:Silicon Dioxide; D004126:Dimethylformamide