Living Crystallization-Driven Self-Assembly of Linear and V-Shaped Oligo(<i>p</i>-phenylene ethynylene)-Containing Block Copolymers: Architecture Effect of π-Conjugated Crystalline Segment
Bibliographic record
Abstract
Diblock copolymers (BCPs) with a π-conjugated block and an appropriate block ratio can undergo crystallization-driven self-assembly (CDSA) to form fiber-like micelles of uniform width and length. Almost all examples in the literature involve BCPs with a linear π-conjugated block. We are interested in exploring the influence of the architecture of the π-conjugated block on (living) CDSA of oligo(p-phenylene ethynylene) (OPE) BCPs with a common block length and the same corona-forming block. Herein, we designed and synthesized three OPE7-b-PNIPAM22 BCPs with seven repeats in the OPE block, PNIPAM = poly(N-isopropylacrylamide), with a mean degree of polymerization of 22 which differed only in the architecture of the OPE block. One sample, the reference, had a linear OPE7 block. A second sample had a V-shaped OPE7 with PNIPAM22 attached in the middle (mV-OPE7), and the third sample was V-shaped with PNIPAM22 attached at one end (tV-OPE7). Self-assembly experiments in ethanol/water mixtures led to micelle-like aggregates. The variation of architecture of OPE7 backbone of OPE7-b-PNIPAM22 led into distinct packing modes and different morphologies of the resulting aggregates. Self-seeding experiments with L-OPE7-b-PNIPAM22 gave monodisperse fiber-like micelles of uniform width and tunable length, whereas irregular aggregates or polydisperse ribbon-like micelles were formed by tV-OPE7-b-PNIPAM22 and mV-OPE7-b-PNIPAM22. Important differences were also found in seeded growth experiments designed to form block comicelles with a heterogeneous core junction. L-OPE7-b-PNIPAM22 could efficiently deposit onto the L-OPE9 core of L-OPE9-b-P2VP56 seed micelles (P2VP = poly(2-vinylpyridine) to form triblock comicelles. In contrast, neither mV-OPE7-b-PNIPAM22 nor tV-OPE7-b-PNIPAM22 was able to grow micelles from the ends of the L-OPE9-b-P2VP56 seed micelles. Instead, they formed polydisperse micelles by a self-nucleation and growth process. This work provides instructive information about how the architecture of π-conjugated blocks affects the CDSA of BCPs with a π-conjugated-polymer block, especially under especially self-seeding and heterogeneous seeded growth protocols.
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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) | 0.001 | 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".