Linear and Branched Fiber-like Micelles from the Crystallization-Driven Self-Assembly of Heterobimetallic Block Copolymer Polyelectrolyte/Surfactant Complexes
Bibliographic record
Abstract
The solution self-assembly of a heterobimetallic diblock copolymer with a crystallizable poly(ferrocenyldimethylsilane) (PFS) core-forming block and a corona-forming segment featuring a poly(cobaltoceniumethylene) (PCE)-based polyelectrolyte/surfactant complex, PFS 50 - b -[PCE][AOT] 50 (AOT = bis(2-ethylhexyl) sulfosuccinate), has been explored. Fiber-like micelles were formed in selective solvents for the Co-containing block, yielding a corona in which every repeat unit bears a charge. We found that key features of the one-dimensional (1D) morphologies were dependent on both the polarity of the solvent medium and temperature. In the most polar of the explored solvent media ( i PrOH), seeded growth from 1D seeds of PFS 50 - b -P2VP 739 (P2VP = poly(2-vinylpyridine)) yielded tapered B-A-B triblock comicelles, where the width of the terminal B region derived from PFS- b -[PCE][AOT] n reduced on moving from the interface with the seed to the micelle termini. In addition, ca. 30% of the micelles featured branching to yield multiple terminal blocks. On reducing the polarity of the solvent medium by the addition of 20% THF, the tapering of the micelles was no longer apparent, and the degree of branching was substantially increased to ca. 100% of the population. With increased amounts of THF (30%), the degree of branching reduced dramatically to ca. 3%. In the least polar medium investigated (1:10 i PrOH/EtOAc), linear triblock comicelles formed in which the terminal blocks were of consistent diameter, with no evidence for tapering or branching. However, significant unsymmetric growth (i.e., a higher degree of growth from one seed terminus compared to the other) was detected. Post self-assembly modification by coronal counterion exchange to alter the chemistry and solubility of the corona was also explored.
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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".