Crystallization-Driven Self-Assembly of Amphiphilic Triblock Terpolymers With Two Corona-Forming Blocks of Distinct Hydrophilicities
Bibliographic record
Abstract
We report the synthesis and studies of self-assembly in solution of two related polyferrocenyldimethylsilane (PFS) ABC triblock terpolymers (TTPs), in which the BC blocks are amphiphilic comb diblock copolymers, PFS27-b-POEGMA180-b-PTDMA178 and PFS27-b-PTDMA181-b-POEGMA166. The subscripts refer to the mean degrees of polymerization. Crystallization-driven self-assembly of these TTPs was studied in four alcohol solvents of decreasing polarity. Poly(tetradecyl methacrylate) (PTDMA) has limited solubility in 1-butanol below 45 °C, whereas POEGMA exhibits upper critical solution temperature (UCST) behavior in 1-hexanol (27 °C), 1-octanol (38 °C), and 1-decanol (42 °C). Consequently, the corona component below its UCST would be in a collapsed or microphase-separated state. PFS27-b-POEGMA180-b-PTDMA178 dissolved in hot 1-hexanol, 1-octanol, and 1-decanol and formed long rodlike micelles upon cooling. Micelle fragments generated by sonication served as seeds for both seeded growth and self-seeding experiments, leading to rodlike micelles of uniform length. PFS27-b-PTDMA181-b-POEGMA166 exhibited similar behavior in 1-butanol. The characteristic that these experiments have in common is that the outer block of the corona exhibits good solubility in the medium. PFS27-b-PTDMA181-b-POEGMA166 in the more hydrophobic alcohols behaved differently. Seeded growth experiments led to raftlike objects made up of 5–10 rodlike micelles of similar length, lined up side-by-side. The length of the rods, and hence the length of the rafts, increased linearly with the unimer-to-seed ratio. Self-seeding experiments with these micelle fragments, particularly in 1-octanol and 1-decanol, also led to raftlike objects built up from uniform rodlike micelle building block. We propose a model for raft formation based on the idea that at T < UCST for the outer POEGMA block, there is an attractive interaction between the corona blocks of the micelles. This attraction is strong enough to promote association but not strong enough to lead to precipitation. Parallel alignment of the adjacent micelles of similar length maximizes the interaction between them.
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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) | 0.000 | 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 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".