Crystallization-Driven Self-Assembly of a Block Copolymer with Amphiphilic Pendant Groups
Bibliographic record
Abstract
Crystalline-coil block copolymers (BCPs) with an amphiphilic corona-forming block broaden the range of solvents in which crystallization-driven self-assembly experiments can be carried out. These materials allow one to examine how rather large changes in solvent polarity can affect the self-assembly process, leading to novel uniform structures. Here, we describe the synthesis and self-assembly properties of a crystalline-brush BCP, PFS 27 - b -P(EG-E)MA 48 (PFS, poly(ferrocenyldimethylsilane), and P(EG-E)MA, poly(tetraethylene glycol monododecyl ether methacrylate); the subscripts refer to the mean degrees of polymerization). Tetrahydrofuran (THF) is a common good solvent for both blocks, whereas the corona polymer itself is soluble in alcohols ranging from 2-propanol to 1-decanol and in octane and decane. Self-assembly in 2-propanol was “normal”, forming long (>5 μm) fiber-like micelles of uniform width when the polymer suspended in solvent was heated (i.e., 80 °C) and cooled. Micelles of similar width but uniform and variable length were obtained when micelle fragments were subjected to seeded growth or self-seeding conditions. In primary alcohols (1-butanol to 1-decanol), direct self-assembly led to uniform scarf-like structures (total length ∼2 μm) in which the length of the central platelet increased with the carbon number in the solvent, offset by shorter fiber-like protrusions at the ends. We speculate that these changes are related to the temperature at which core crystallization occurred as the samples cooled. Self-assembly in decane was more complicated. Large (>10 μm) aggregated structures consisting of fiber bundles formed initially. Sonication followed by seeded growth with additional BCP or self-seeding led to relatively uniform elongated lenticular micelles, substantially wider than those formed under these protocols for this BCP in 2-propanol. Solvent polarity has a profound effect on the self-assembly of this BCP with a brush-like amphiphilic corona-forming block.
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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".