1. Structure and thermodynamics of mixed polymeric micelles with crystalline cores: tuning properties via co-assembly
- Author
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Nico König, Reidar Lund, and Lutz Willner
- Subjects
chemistry.chemical_classification ,Work (thermodynamics) ,Materials science ,Aggregation number ,Aqueous solution ,Thermodynamics ,02 engineering and technology ,General Chemistry ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Condensed Matter Physics ,01 natural sciences ,Micelle ,0104 chemical sciences ,Crystallinity ,Differential scanning calorimetry ,chemistry ,0210 nano-technology ,Melting-point depression ,Alkyl - Abstract
We investigate micelles formed by mixtures of n-alkyl-poly(ethylene oxide) block copolymers, Cn-PEO, with different alkyl block lengths in aqueous solution. This model system has previously been used to shed light on the interplay between exchange kinetics and crystallinity in self-assembling systems [König et al., Phys. Rev. Lett., 2019, 122, 078001]. Now we report on the structure and thermodynamics of these micelles by combining results from small-angle X-ray scattering, differential scanning calorimetry and volumetric measurements. We show that mixed micelles are formed despite the fact that length-mismatched n-alkanes of similar weights in bulk tend to demix below the crystallization temperature. Instead, the system exhibits similar properties as single-component micelles but with a modulated melting region. Interestingly, the melting point depression due to self-confinement within the micellar core can be approximately described by a generalized Gibbs-Thomson equation, similar to single-component micelles [Zinn et al. Phys. Rev. Lett., 2014, 113, 238305]. Furthermore, we find a novel scaling law for these micelles where, at least for larger n, the aggregation number scales with the third power of the length of the hydrophobic block, Nagg ∝ n3. Possibly, there might be a cross-over from the conventional Nagg ∝ n2 behaviour around n ≈ 19. However, the reason for such a transition as well as the strong n dependence remains a challenge and requires more theoretical work.
- Published
- 2019
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