Journal
MACROMOLECULES
Volume 46, Issue 15, Pages 6319-6325Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ma4007544
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Funding
- EPSRC
- University of Warwick
- Birmingham Science City
- Advantage West Midlands
- European Regional Development Fund
- National Institute of General Medical Sciences of the National Institutes of Health (NIH) [P20GM103541]
- Department of Defense, Air Force Office of Scientific Research, National Defense Science and Engineering Graduate (NDSEG) Fellowship [32 CFR 168a]
- NIST, U.S. Department of Commerce [70NANB7H6178]
- EPSRC [EP/F01645X/2, EP/G004897/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/F01645X/2, EP/G004897/1] Funding Source: researchfish
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We report the aqueous solution self-assembly of a series of poly(N-isopropylacrylamide) (PNIPAM) polymers end-functionalized with a hydrophobic sulfur-carbon-sulfur (SCS) pincer ligand. Although the hydrophobic ligand accounted for <5 wt % of the overall homopolymer mass, the polymers self-assembled into well-defined spherical micelles in aqueous solution, and these micelles are potential precursors to solution-assembled nanoreactors for small molecule catalysis applications. The micelle structural details were investigated using light scattering, cryogenic transmission electron microscopy (cryo-TEM), and small angle neutron scattering (SANS). Radial density profiles extracted from the cryo-TEM micrographs suggested that the PNIPAM chains formed a diffuse corona with a radially decreasing corona density profile and provided valuable a priori information about the micelle structure for SANS data modeling. SANS analysis indicated a similar profile in which the corona surrounded a small hydrophobic core containing the pincer ligand. The similarity between the SANS and cryo-TEM results demonstrated that detailed information about the micelle density profile can be obtained directly from cryo-TEM and highlighted the complementary use of scattering and cryo-TEM in the structural characterization of solution assemblies, such as the SCS pincer-functionalized homopolymers described here.
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