Synthesis of Stimuli-responsive, Water-soluble Poly[2-(dimethylamino)ethyl methacrylate/styrene] Statistical Copolymers by Nitroxide Mediated Polymerization
Why this work is in the frame
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Bibliographic record
Abstract
2-(Dimethylamino)ethyl methacrylate/styrene statistical copolymers (poly(DMAEMA-stat-styrene)) with feed compositions fDMAEMA = 80–95 mol%, (number average molecular weights Mn = 9.5–11.2 kg mol−1) were synthesized using succinimidyl ester-functionalized BlocBuilder alkoxyamine initiator at 80 °C in bulk. Polymerization rate increased three-fold on increasing fDMAEMA = 80 to 95 mol%. Linear Mn increases with conversion were observed up to about 50% conversion and obtained copolymers possessed monomodal, relatively narrow molecular weight distributions (polydispersity = 1.32–1.59). Copolymers with fDMAEMA = 80 and 90 mol% were also cleanly chain-extended with DMAEMA/styrene mixtures of 95 and 90 mol% DMAEMA, respectively, confirming the livingness of the copolymers. Copolymer phase behavior in aqueous solutions was examined by dynamic light scattering and UV-Vis spectroscopy. All copolymers exhibited lower critical solution temperature (LCST)-type behavior. LCST decreased with increasing styrene content in the copolymer and with increasing solution concentration. All copolymers were completely water-soluble and temperature insensitive at pH 4 but were more hydrophobic at pH 10, particularly copolymers with fDMAEMA = 80 and 85 mol%, which were water-insoluble. At pH 10, LCST of copolymers with fDMAEMA = 90 and 95 mol% were more than 10 °C lower compared to their solutions in neutral, de-ionized water. Block copolymers with two statistical blocks with different DMAEMA compositions exhibited a single LCST, suggesting the block segments were not distinct enough to exhibit separate LCSTs in water.
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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) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.014 | 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 it