Influence of Double Hydrogen Bonds and Alkyl Chains on the Gelation of Nonchiral Polyurethane Model Compounds: Sheets, Eaves Trough, Tubes and Oriented Fibers
Bibliographic record
Abstract
We describe the gelation, upon self-assembly of a series of nonchiral molecules, resulting in tubular morphology of the fibers. These are biscarbamates, which are model compounds for polyurethanes with two hydrogen bonding groups separated by a (CH(2))(6) spacer and symmetrically substituted with alkyl chains on either side varying in length from C(6) to C(18). Upon gelation, these molecules form a sheet initially. The sheets then tend to wrap, leading to tubules. Those with partial wrapping resemble eaves troughs. With the predominant growth along the hydrogen bonding direction, the energy of interaction between the molecules along this direction would be more dominant than just the van der Waals interaction in the other two, leading to asymmetry of interaction in the sheet. We rationalize such tube formation in this case on the basis of the theories [Schnur, J. M.; Ratna, B. R.; Selinger, J. V.; Singh, A.; Jyothi, G.; Easwaran, K. R. K. Science, 1994, 264, 945. Schnur, J. M. Science, 1993, 262, 166. McKierman, R. L.; Heintz, A. M.; Hsu, S. L.; Gido, S. P.; Penelle, J. Polym. Mater. Sci. Eng. 2001, 84, 416.] which were developed for amphiphilic mono and bilayers, which state that these bilayers are not at their minimal energy when they are flat, and prefer a bent state. The gelation behavior of this series with double hydrogen bond is compared with the monocarbamates with a single hydrogen bonding motif [Moniruzzaman, M.; Sundararajan, P. R. Langmuir 2005, 21, 3802.]. We attribute the tendency toward both gelation and crystallization in some cases to the competing contributions of the hydrogen bond and van der Waals interactions between the long alkyl side chains. Oriented fibers for X-ray diffraction were obtained by simply using a magnetic stir bar during gelation. It is also found that the solvents that gel with diureas [van Esch, J.; Kellogg, R. M.; Feringa, B. L. Tetrahedron Lett. 1997, 38, 281] also form gels with biscarbamates. While the biscarbamates with even number of CH(2) groups in the side chain form short fibers, one with (CH(2))(9) side group formed long fibers characteristic of organo gels. In addition, when this odd side chain biscarbamate was mixed with one having a (CH(2))(8) side group, the gelation led to long fibers, following the sergeant and soldier principle.
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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 | 0.000 | 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) | 0.000 | 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 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".