Crystallization-Driven Solution Self-Assembly of μ-ABC Miktoarm Star Terpolymers with Core-Forming Polyferrocenylsilane Blocks
Bibliographic record
Abstract
A comparative study of the solution self-assembly behavior of two polystyrene- arm -polyisoprene- arm -polyferrocenylsilane (μ-SIF) miktoarm star terpolymers of similar composition has been conducted: one with a short, atactic, noncrystallizable poly(ferrocenylethylmethylsilane) (PFEMS) block (μ-SIF a ) and one with a short, crystallizable poly(ferrocenyldimethylsilane) (PFDMS) block (μ-SIF c ). Both solvent composition and the amorphous/crystallizable nature of the polyferrocenylsilane (PFS) block exhibited a profound influence on the morphologies of the micelles obtained. In hexane, the formation of uniform spherical micelles with an amorphous, phase-mixed PS/PFS core was observed for both μ-SIF a and μ-SIF c . The introduction of cyclohexane (a theta-solvent for PS at 34.5 °C) to give a 1:1 cyclohexane/hexane (v/v) solvent composition resulted in the formation of distorted spherical micelles with a core composed of phase-separated PS and PFS, for both μ-SIF a and μ-SIF c . Interestingly, the distorted spherical micelles formed from crystallizable μ-SIF c evolved with time into elongated fiber-like structures with a phase-separated PS and PFDMS core, while the noncrystallizable counterpart, μ-SIF a, remained as distorted spheres. It was found that in ethyl acetate, a good solvent for PI and PS, μ-SIF a remained unimeric in solution, whereas μ-SIF c formed cylindrical micelles composed of a crystalline PFDMS core and a phase-separated, patchy, PS and PI corona. Finally, seeded growth of μ-SIF c from short, cylindrical PFDMS- b -PDMS seeds (PDMS = polydimethylsiloxane) was demonstrated, yielding B–A–B block comicelles where outer segments derived from μ-SIF c blocks bore a strong resemblance to that ultimately formed under conditions of homogeneous nucleation.
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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) | 0.001 | 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 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".