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Spatio-temporal heterogeneities in nanosegregated single-molecule polymeric nanoparticles
Petra Bačová1, Emmanouil Glynos2, Spiros H Anastasiadis3
1Institute of Applied and Computational Mathematics (IACM), Foundation for Research and Technology Hellas (FORTH), GR-70013 Heraklion, Crete, Greece. pbacova@iacm.forth.gr.
Soft Matter
|April 21, 2020
Summary
Dynamical heterogeneities in nanostructured star copolymers are influenced by their internal morphology. Geometric constraints near the core create distinct polymer dynamics compared to regions further away.
Area of Science:
- Polymer science
- Materials science
- Nanotechnology
Background:
- Understanding structure-dynamics relationships in nanostructured materials is key for designing advanced hybrid materials.
- Mikto-arm star copolymers offer unique nanostructured morphologies due to their distinct polymer arms.
Purpose of the Study:
- To investigate the intramolecular dynamical heterogeneities in nanostructured single-molecule nanoparticles composed of poly(ethylene oxide) (PEO) and polystyrene (PS) arms.
- To correlate the observed dynamical heterogeneities with the internal morphology (Janus-like or patchy-like) of the nanoparticles.
Main Methods:
- Atomistic molecular dynamics simulations were employed to analyze the behavior of the copolymer nanoparticles.
- The simulations focused on examining the local environments and segmental dynamics within the nanoparticles.
Main Results:
- Nanoparticles exhibited distinct "Janus-like" or "patchy-like" morphologies based on star functionality.
- Strong intramolecular dynamical heterogeneities were observed, driven by differences in the local polymer environment.
- Near the star core, geometric constraints led to unfavorable PEO:PS contacts, mimicking dynamically asymmetric blends.
- Away from the core, nanosegregation resulted in segmental dynamics comparable to homopolymer star analogues.
Conclusions:
- The internal nanostructure of mikto-arm star copolymers significantly dictates their dynamical properties.
- Local environments, particularly near the star core, play a crucial role in segment dynamics.
- These findings provide insights into the design principles for hybrid materials with tunable properties based on copolymer architecture.
