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, PFS50-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 (iPrOH), seeded growth from 1D seeds of PFS50-b-P2VP739 (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 iPrOH/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 distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| 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) | 0.001 | 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 teacher head, 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".