Fluorescent, Thermoresponsive Oligo(ethylene glycol) Methacrylate/9-(4-Vinylbenzyl)-9<i>H</i>-carbazole Copolymers Designed with Multiple LCSTs via Nitroxide Mediated Controlled Radical Polymerization
Bibliographic record
Abstract
9-(4-Vinylbenzyl)-9 H -carbazole (VBK) was used as the “controlling” comonomer for nitroxide mediated polymerization with 10 mol % SG1 free nitroxide relative to BlocBuilder initiator at 80 °C of oligo(ethylene glycol) methyl ether methacrylate (8–9 ethylene glycol (EG) units) (OEGMA 8–9 ), 2-(2-methoxyethoxy)ethyl methacrylate (MEO 2 MA) and for an OEGMA 8–9 /MEO 2 MA-mixed feed. The synthesis of MEO 2 MA/VBK and OEGMA 8–9 /VBK copolymers and MEO 2 MA/OEGMA 8–9 /VBK terpolymers exhibited linear increases in number-average molecular weight ( M̅ n ) versus conversion X, up until X = 0.6, with final copolymers characterized by relatively narrow, monomodal molecular weight distributions ( M̅ w / M̅ n < 1.4, in most cases). A series of MEO 2 MA/OEGMA 8–9 /VBK terpolymers were synthesized and by varying the OEGMA 8–9:MEO 2 MA feed ratios, the terpolymers exhibited tunable lower critical solution temperatures in water (28 °C < LCST s < 81 °C). MEO 2 MA/OEGMA 8–9 /VBK terpolymers were deemed sufficiently pseudo-“living” to reinitiate a second batch of MEO 2 MA/OEGMA 8–9 /VBK, with few apparent dead chains, as indicated by the monomodal shift in the GPC chromatograms. The resulting MEO 2 MA/OEGMA 8–9 /VBK block copolymers were designed so that each block exhibited a distinct LCST, which was confirmed by UV–vis and dynamic light scattering. In addition to controlling the terpolymerization, the VBK units imparted thermo-responsive fluorescence into the final copolymers.
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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".