Thermo-Reversible Gelation Of Rod-Coil and Coil-Rod-Coil Molecules Based on Perylene Diimides
Bibliographic record
Abstract
Polymer gelation is a route to obtain highly organized morphologies.The aim of my thesis was to study the physical gelation of covalently attached perylene diimide (PDI) polymers during their self-assembly.With the gelators used, chain entanglement and network formation trap the solvent causing gelation.Hence, forces such as hydrogen bonding are not a requirement.We first describe the thermo-reversible gelation of PDMS via the physical route, without any functionalization.We discuss a solvent system, propylamine or hexylamine, gelled by PDMS, without any filler, catalysts or chemical crosslinks.The simple route to the physical gelation of PDMS was then extended to preparing PDMS attached PDI based gels.Morphological studies showed that of mono-substituted PDI (Mono-PDMS) gels consist of hollow spheres while disubstituted PDI (Di-PDMS) gels consist of ribbons that are folded along the length into an eaves trough.We attributed this gelation to the entanglement of the PDMS, in addition to the πinteraction mediated self-assembly of the perylene segments.We then continued our work with PDI attached to a water-soluble side chain; here we studied the gelation of PDI, substituted with Jeffamine® on one imide nitrogen (MJ-PTCDI) or both (DJ-PTCDI).As with the Di-PDMS and Mono-PDMS, the DJ-PTCDI is a Gemini surfactant and MJ-PTCDI is an inverse macromolecular surfactant.Previous studies in our group showed that self-assembly of the PDI was seen in water and aqueous solvent mixtures, but not in the other non-aqueous solvents.In the present case, the morphology of the gels depended on the amount of solvent: non-solvent ratio.Morphological studies showed that although fibers are not seen for DJ-PTCDI gels, the "chaining" of the spheres seems to be present.The SEM image of the cross section of the MJ-PTCDI sample shows the honeycomb morphology similar to that of DJ-PTCDI.Thus with MJ-PTCDI based gels also, the worm-like vesicular morphology occurs.Formation of worm-like PTCDI Perylene-3,4,9,10-tetracarboxylic diimide MJ-PTCDI Mono Jeffamine monoisopropyl perylene tetracarboxylicacid diimide DJ-PTCDI Jeffamine perylene tetracarboxylicacid diimide FT-IR NMR Fourier Transform Infrared Spectroscopy Nuclear Magnetic Resonance Spectroscopy Å angstroms or 1x10 -10 meters PS Polystyrene PS-PTCDI-PS Polystyrene perylene tetracarboxylicacid diimide M w Weight average molecular weight OM Optical Microscopy SEM Scanning Electron Microscopy µm micrometer nm nanometers DSC Differential Scanning Calorimetry
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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".