期刊
MACROMOLECULES
卷 53, 期 23, 页码 10686-10698出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.macromol.0c01936
关键词
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资金
- Research Council of Norway
- Norwegian NMR Platform, NNP [226244/F50]
- Department of Chemistry and the Faculty of Mathematics
- Natural Sciences at University of Oslo
- European Union [731019]
Self-assembly of amphiphilic polymers into micelles is an archetypical example of a self-confined system due to the formation of micellar cores with dimensions of a few nanometers. In this work, we investigate the chain packing and resulting shape of C-n-PEOx micelles with semicrystalline cores using small/wide-angle X-ray scattering (SAXS/WAXS), contrast-variation small-angle neutron scattering (SANS), and nuclear magnetic resonance spectroscopy (NMR). Interestingly, the n-alkyl chains adopt a rotator-like conformation and pack into prolate ellipses (axial ratio epsilon approximate to 0.5) in the crystalline region and abruptly arrange into a more spheroidal shape (e approximate to 0.7) above the melting point. We attribute the distorted spherical shape above the melting point to thermal fluctuations and intrinsic rigidity of the n-alkyl blocks. We also find evidence for a thin dehydrated PEO layer (<= 1 nm) close to the micellar core. The results provide substantial insight into the interplay between crystallinity and molecular packing in confinement and the resulting overall micellar shape.
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