Photo Nitroxide-Mediated Living Radical Polymerization of Hindered Amine-Supported Methacrylate
Bibliographic record
Abstract
With the aim of obtaining giant polymer vesicles supporting a hindered amine that is converted into a redox catalyst on the vesicle shells, the living nature of the photo nitroxide-mediated living radical polymerization (photo NMP) of a monomer containing a hindered amine and the formation of the vesicles consisting of an amphiphilic diblock copolymer by the polymerization-induced self-assembly were investigated. The photo NMP of 2,2,6,6-tetramethyl-4-piperidyl methacrylate (TPMA) was performed in methanol using 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) as the mediator, 2,2’-azobis[2-(2-imidazolin-2-yl)propane] (V-61) as the initiator, and (4-tert-butylphenyl)diphenylsulfonium triflate as the accelerator by UV irradiation at room temperature. The first-order time-conversion plots had an induction period in which the MTEMPO molecules were captured by the initiator radicals and the monomer radicals generated by the initiation. It was confirmed that the polymerization proceeded by a living mechanism based on linear correlations of the molecular weight of the poly(TPMA) (PTPMA) versus the monomer conversion and the reciprocal of the initial concentration of V-61. Based on the livingness of the polymerization, the photo NMP-induced self-assembly for the block copolymerization of methyl methacrylate (MMA) using the PTPMA end-capped with MTEMPO was carried out in methanol to produce microsized giant spherical vesicles consisting of the amphiphilic PTPMA-block-poly(MMA) diblock copolymer. A differential scanning calorimetry study demonstrated that the vesicles had a single bilayer structure.
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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 | 0.003 | 0.002 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.001 | 0.003 |
| Science and technology studies | 0.000 | 0.002 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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".