Supramolecular Organometallic Polymer Chemistry: Multiple Morphologies and Superstructures from the Solution Self-Assembly of Polyferrocene-block-Polysiloxane-block-Polyferrocene Triblock Copolymers
Bibliographic record
Abstract
The solution self-assembly of an organometallic-inorganic triblock copolymer, poly(ferrocenyldimethylsilane)-block-poly(dimethylsiloxane)-block-poly-(ferrocenyldimethylsilane) (PFDMS-b-PDMS-b-PFDMS, 3b; block ratio 1:13:1; Mn = 2.88 x 10(4) gmol(-1), polydispersity (PDI) 1.43 (gel permeation chromatography, GPC)) was studied in n-hexane, a PDMS block selective solvent. Transmission electron microscopy (TEM), atomic force microscopy (AFM), and TEM with negative staining analysis of these micellar solutions after solvent evaporation revealed the presence of multiple micellar morphologies including spheres, cylinders, and novel flower-like supramolecular aggregates. TEM analysis of samples fractionated by ultracentrifugation and preparative size-exclusion chromatography suggest that the formation of multiple morphologies is a consequence of compositional variations. When micellar solutions were prepared at 50 degrees C (above the glass transition of the PFDMS core-forming block) flower-like micellar aggregates similar to those present in micellar solutions prepared at room temperature also formed. However, after solvent evaporation, TEM analysis of micellar solutions prepared in decane at about 150 degrees C, above the melt temperature of the PFDMS core (ca. 120-145 degrees C), revealed the presence of spherical micelles (when decane solutions at 150 degrees C were rapidly cooled to room temperature) and rod-like cylindrical micelles (when decane solutions at 150 degrees C were slowly cooled to room temperature). In contrast, poly(ferrocenylmethylethylsilane)block-poly(dimethylsiloxane)-block-poly(ferrocenylmethylethylsilane) (PFMES-b-PDMS-b-PFMES, 4; block ratio 1:16:1; Mn=2.90x10(4)g mol(-1), PDI= 1.42 (GPC)) and poly(ferrocenylmethylphenylsilane)-block-poly(dimethylsiloxane)-block-poly(ferrocenylmethylphenylsilane) (PFMPS-b-PDMS-b-PFMPS, 5; block ratio 1:15:1; Mn=3.00 x 10(4) gmol(-1), PDI = 1.38 (GPC)), which possess completely amorphous organometallic core-forming blocks, formed only spherical micelles in hexane at room temperature. These observations indicate that crystallinity of the insoluble polyferrocenylsilane block is a critical factor in the formation of the nonspherical micelle morphologies.
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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".