Asymmetric Giant “Bolaform-like” Surfactants: Precise Synthesis, Phase Diagram, and Crystallization-Induced Phase Separation
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Bibliographic record
Abstract
A series of unique heterofunctionalized asymmetric giant “bolaform-like” surfactants composed of a polystyrene (PS) chain end-capped with two distinctly functionalized polyhedral oligomeric silsesquioxane (POSS) cages [one with seven isobutyl groups (BPOSS) and the other with 14 hydroxyl groups (DPOSS)] were designed and synthesized, and their self-assembly behaviors were investigated. Combining the atomic transfer radical polymerization using a BPOSS-containing initiator and the sequential “click” approach, BPOSS-PS n -DPOSS samples with different PS molecular weights were obtained. Investigation on their self-assembly behaviors revealed that they could form a variety of different ordered structures, such as lamellae, double gyroids, hexagonally packed cylinders, and body-center-cubic spheres, with feature sizes around or below 10 nm. Functional groups on the POSS cages govern the interaction parameters of different POSS cages with the PS interconnect and thus their compatibility. Hydrophilic DPOSS cages are phase-separated from the PS domains, while BPOSS cages are favorably associated within the PS domains. However, in the lamellae phase where the geometry of confinement seems compatible with the close-packing of BPOSS, the BPOSS cages tend to crystallize due to the existence of the flat interfaces, leading to further phase separation of the BPOSS cages from the PS interconnects. These results provide insights into the design of novel self-assembling materials based on POSS–polymer conjugates toward desired physical properties.
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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 | 0.001 |
| 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) | 0.000 | 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