Understanding the self-assembly behavior of polymers of various topologies is key to a reliable design of functional polymer materials. Self-assembly under confinement conditions emerges as a versatile avenue to design polymer particles with complex internal morphologies while simultaneously facilitating scale-up. However, only linear block copolymers have been studied to date, despite the increasing control over macromolecule composition and architecture available. This study extends the investigation of polymer self-assembly in confinement from regular diblock copolymers to diblock molecular polymer brushes (MPBs). Block-type MPBs with polystyrene (PS) and polylactide (PLA) compartments of different sizes are incorporated into surfactant-stabilized oil-in-water (chloroform/water) emulsions. The increasing confinement in the nanoemulsion droplets during solvent evaporation directs the MPBs to form solid nano/microparticles. Microscopy studies reveal an intricate internal particle structure, including interpenetrating networks and axially stacked lamellae of PS and PLA, depending on the PS/PLA ratio of the brushes.
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http://dx.doi.org/10.1002/marc.201800177 | DOI Listing |
J Chem Phys
January 2025
School of Chemistry, Beihang University, Beijing 100191, China.
Dynamic density functional theory (DDFT) is a fruitful approach for modeling polymer dynamics, benefiting from its multiscale and hybrid nature. However, the Onsager coefficient, the only free parameter in DDFT, is primarily derived empirically, limiting the accuracy and broad application of DDFT. Herein, we propose a machine learning-based, bottom-up workflow to directly extract the Onsager coefficient from molecular simulations, circumventing partly heuristic assumptions in traditional approaches.
View Article and Find Full Text PDFSoft Matter
January 2025
Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, NO-0315 Oslo, Norway.
Due to the escalating threat of the pathogens' capability of quick adaptation to antibiotics, finding new alternatives is crucial. Although antimicrobial peptides (AMPs) are highly potent and effective, their therapeutic use is limited' as they are prone to enzymatic degradation, are cytotoxic and have low retention. To overcome these challenges, we investigate the complexation of the cationic AMP colistin with diblock copolymers poly(ethylene oxide)--poly(methacrylic acid) (PEO--PMAA) forming colistin-complex coacervate core micelles (colistin-C3Ms).
View Article and Find Full Text PDFAdv Mater
January 2025
Príncipe Felipe Research Center, Polymer Therapeutics Lab., Valencia, 46012, Spain.
Mitochondria play critical roles in regulating cell fate, with dysfunction correlating with the development of multiple diseases, emphasizing the need for engineered nanomedicines that cross biological barriers. Said nanomedicines often target fluctuating mitochondrial properties and/or present inefficient/insufficient cytosolic delivery (resulting in poor overall activity), while many require complex synthetic procedures involving targeting residues (hindering clinical translation). The synthesis/characterization of polypeptide-based cell penetrating diblock copolymers of poly-L-ornithine (PLO) and polyproline (PLP) (PLO-PLP, n:m ratio 1:3) are described as mitochondria-targeting nanocarriers.
View Article and Find Full Text PDFACS Nano
January 2025
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, United States.
J Chem Phys
January 2025
School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, China.
Diblock copolyelectrolytes have significant potential in applications such as solid-state single-ion conductors, but precisely controlling their nanostructures for efficient ion transport remains a challenge. In this study, we explore the phase behavior and microphase transitions of AX BY-type diblock copolyelectrolytes under alternating electric fields using coarse-grained molecular dynamics simulations. We systematically investigate the effects of various electric field features, including unipolar and bipolar square-waves, as well as offset and non-offset sine-waves, focusing on how field strength and period influence the self-assembling morphology of the copolyelectrolytes.
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