Self-Sorting Sergeant-Soldier, and Majority Rules Phenomena in Crystals and Gels of Polyurethane Model Compounds
Bibliographic record
Abstract
Hydrogen bond-mediated self-assembling biscarbamates have been studied by our group as model compounds of polyurethanes with respect to the crystallization and gelation behaviour in both solid state and solution phase respectively.The aim of my thesis is to investigate the effects on the blending and the gelation of biscarbamates with different alkyl side chain lengths.Melt blending of these molecules shows molecular selectivity and self-sorting behaviour leading to immiscibility.We revealed that the difference in the growth rates of the individual species is responsible for the self-sorting behaviour in these non-chiral synthetic compounds.We discussed methods to bridge the self and non-self that would lead to a more homogeneous system.The gelation properties of biscarbamates with an odd number of carbon atoms in the alkyl side chains, such as the critical gelation concentration, gelation time, gelation temperature, and morphology of the gel fibres were examined.Biscarbamates show odd-even effects in their thermal and gelation behaviours as a function of carbon atom parity in the alkyl side chains in a similar manner to their crystallization behaviours.The blending of the biscarbamate gels shows three different types of blending behaviours.The C8/C9 blend and any gel blends composed of a biscarbamate smaller than C6 display the sergeant-soldier behaviour.The majority rules principle was observed for odd-odd gels blends with an intermediate difference in side chain length.The odd-odd gels blends with a small difference in side chain length self-sort.Organogels with a series of biscarbamates as gelators were prepared using microwave (MW) heating source as well as conventional heating.Biscarbamates with alkyl side chain lengths varying from C5 to C18 were used, with six solvents having dipole moments ranging from 0.07 to 4.3D.The minimum gelation concentration and the amount of heating for ii dissolution were significantly reduced with MW heating with benzonitrile, compared to the conventional heating for all the side chain lengths of the biscarbamates.MW heating is found to be effective with solvents possessing large dipole moments.Although the gels consist of fibers using both methods, an inherent orientation of these fibers was seen with MW heating versus conventional heating methods.
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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".