Branched Micelles by Living Crystallization-Driven Block Copolymer Self-Assembly under Kinetic Control
Bibliographic record
Abstract
We have found that the width and shape (from rectangular to elliptical, to almost circular in cross-section) of the crystalline core of fiberlike micelles of polyferrocenyldimethylsilane (PFDMS) diblock copolymers can be varied by altering the degree of polymerization of PFDMS, and also the chemistry of the complementary corona-forming block. This enabled detailed studies of living crystallization-driven self-assembly (CDSA) processes that involved the addition of unimers with a short, crystallizable core-forming PFDMS block to a seed solution of short micelles with a large diameter crystalline core, derived from block copolymers with a longer PFDMS block. The morphology of resultant micelles was found to be highly dependent on the polarity of the solvent and temperature. For example, linear micelles were formed in less polar solvents (which are moderately poor solvents for PFDMS) and/or at higher temperatures. In contrast, the formation of branched structures could be "switched on" when the opposite conditions were used. Thus, the use of more polar solvents (which are very poor solvents for PFDMS) and ambient or subambient temperatures allowed the formation of branched micelles and block comicelles with variable and spatially distinct corona chemistries, including amphiphilic nanostructures. Rapid crystallization of added unimers at the seed micelle termini under nonequilibrium self-assembly conditions appears to facilitate the formation of the branched micellar structures as a kinetically trapped morphology. This is evidenced by the transformation of the branched micelles into linear micelles on heating at elevated temperatures.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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".