Three-Dimensional Polymer Micelles Formed by Crystallization-Driven Self-Assembly
Bibliographic record
Abstract
on living crystallization-driven self-assembly (CDSA) of amphiphilic block copolymers featuring a crystalline core-forming block. This study focused on polyferrocenylsilane block copolymers (PFS BCPs). Living CDSA operates similarly to living polymerization, enabling the precise fabrication of micelles with predictable shapes and dimensions. The crystalline nature of the core-forming block promotes the formation of structures with low interfacial curvature, such as cylinders and platelets, which are rarely formed in traditional self-assembly techniques based on microphase separation.Over the past two decades, we have pioneered a range of strategies to create one-dimensional (1D), 2D, 3D, and hierarchical uniform PFS BCP structures via CDSA. This method has also been extended to other semicrystalline polymer systems to produce regular and uniform assemblies. While 1D and 2D micelles have been extensively studied, the fabrication of 3D structures remains relatively rare. Nature, however, possesses exquisite 3D structures. Although CDSA has generated some 3D structures, it has not yet achieved the complexity found in nature. Researchers continue to push boundaries toward creating more intricate 3D structures.In this Account, we summarize our research advancements on 3D structure fabrication via CDSA. The free energy of the system, influenced by various factors, ultimately determines micellar morphology and growth behavior. Our work has led to the formation of branched structures through multistep seeded growth processes, incorporating PFS homopolymers (HP) with PFS BCP, manipulating the cooling rate, adjusting the corona block composition, controlling polymer dispersity, and varying solvents. Further innovations involved the use of organic sacrificial templates to produce hollow fiber-basket polymersomes and the application of inorganic substrates for surface micelle growth, yielding organic-inorganic hybrid materials with tailored functionalities. A significant breakthrough was the development of protocols for generating uniform polymeric spherulites and their precursors in solution. Although spherulites are common in bulk polymer materials and materials found in fields such as geology and biology, they have not been observed from block polymers in solution. We uncovered a novel CDSA mechanism in which defects in lamellar precursors act as a critical driver for constructing 3D architectures. To achieve intricate, bioinspired, and uniform 3D structures, further efforts will focus on enhancing structural control and integrating multifunctional properties.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".