Fabrication of Two Types of Shell-Cross-Linked Micelles with “Inverted” Structures in Aqueous Solution from Schizophrenic Water-Soluble ABC Triblock Copolymer via Click Chemistry
Bibliographic record
Abstract
A well-defined ABC triblock copolymer, poly(2-(2-methoxyethoxy)ethyl methacrylate)-b-poly(2-(dimethylamino)ethyl methacrylate)-b-poly(2-(diethylamino)ethyl methacrylate) (PMEO2MA-b-PDMA-b-PDEA), was synthesized via sequential atom transfer radical polymerization using ethyl 2-bromoisobutyrate as the initiator. Reacting the triblock precursor with propargyl bromide in anhydrous tetrahydrofuran yielded PMEO2MA-b-P(DMA-co-QDMA)-b-PDEA triblock copolymer with "clickable" moieties, where QDMA was quaternized DMA residues. PMEO2MA-b-P(DMA-co-QDMA)-b-PDEA triblock copolymer exhibited "schizophrenic" micellization behavior in aqueous solution, forming three-layer onion-like PMEO2MA-core and PDEA-core micelles upon proper adjustment of the solution pH and temperature. For temperature-induced formation of PMEO2MA-core micelles at acidic pH, the critical micellization temperature can be tuned by incorporating oligo(ethylene glycol) methyl ether methacrylate (OEGMA; the mean degree of polymerization was 8-9) residues into the PMEO2MA block, shifting from 38 to 43 degrees C as the OEGMA contents varied in the range of 0-10 mol %. In both types of micelles, the inner shell layer consisted of the middle P(DMA-co-QDMA) segment. Subsequently, cross-linking with tetra(ethylene glycol) diazide via click chemistry in the presence of copper catalysts led to the facile preparation of two types of shell-cross-linked (SCL) micelles with "inverted" structures in purely aqueous solution. The cores and coronas of SCL micelles exhibited multiresponsive swelling/shrinking and collapse/aggregation behavior, respectively. To the best of our knowledge, this represents the first report of the fabrication of two types of SCL micelles with inverted structures from a single schizophrenic water-soluble triblock copolymer in purely aqueous solution.
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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".