Probing the Analogy between Living Crystallization-Driven Self-Assembly and Living Covalent Polymerizations: Length-Independent Growth Behavior for 1D Block Copolymer Nanofibers
Bibliographic record
Abstract
Living crystallization-driven self-assembly (CDSA) is of growing interest as a seeded growth route to colloidally stable one-dimensional (1D) and two-dimensional (2D) nanoparticles and more complex hierarchical assemblies with low size dispersity and predetermined dimensions from crystallizable polymeric and molecular amphiphiles. The origin of the low size dispersities has previously been explained in terms of an analogy between living CDSA with living covalent polymerizations of molecular monomers, in particular, for the case where initiation is faster than propagation and chain terminating or chain breaking processes are absent. Recently, based on Brownian dynamics simulations, an alternative explanation for this behavior involving length-dependent growth has been suggested for 1D fiber-like micelle formation where the growth rate decreases as the length increases. Herein, we have investigated this possibility experimentally by comparing the simultaneous growth from relatively short (Ln = ca. 100 nm) and long (Ln = ca. 1000 nm) seed fibers derived from crystallizable poly(ferrocenyldimethylsilane) (PFS) block copolymers with polar or nonpolar corona-forming blocks. Using a statistical analysis of fiber lengths based on transmission electron microscopy (TEM) data, we found that the growth rate from the termini of the short and long fibers was identical within experimental error in either polar or nonpolar media at both ambient (22 °C) and elevated (35 °C) temperatures. Analogous length-independent growth was found for the case of the formation of fiber-like triblock comicelles and for 1D micelles with a different, crystallizable poly(fluorenetrimethylenecarbonate) (PFTMC) core-forming block. The results therefore strongly indicate that the low dispersities characteristic of living CDSA processes do not arise from a gradual reduction in growth rate with fiber length. The length-independent growth observed experimentally is therefore consistent with the previously proposed explanation for length control and low dispersities based on an analogy with living covalent polymerizations of molecular monomers.
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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 | 0.001 | 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".