Molar Absorbance Coefficient of Pyrene Aggregates in Water Generated by a Poly(ethylene oxide) Capped at a Single End with Pyrene
Bibliographic record
Abstract
The molar absorbance coefficient of ground-state pyrene aggregates (ε(E0)(λ)) in water generated by a short poly(ethylene oxide) chain labeled at a single end with a 1-pyrenemethoxide unit, namely, the polymeric construct Py₁-PEO(2.5K), was determined by a combination of UV-vis absorption and time-resolved fluorescence experiments. Since direct excitation of ground-state pyrene aggregates results in instantaneous excimer emission, whereas excimer formation by diffusive encounters between an excited- and a ground-state pyrene is delayed, acquisition of a pyrene monomer and excimer fluorescence decays with 1 nm increments of the excitation wavelength can probe the subtle effect that the excitation wavelength has on the extent of instantaneous excimer formation. These differences were taken advantage of to determine the fraction f(agg)(f)(λ) of the total absorbance of the Py₁-PEO(2.5K) solution that is due to ground-state pyrene aggregates. This was achieved by fitting the pyrene monomer and excimer fluorescence decays globally with the model free analysis. For each wavelength, an f(agg)(f)(λ) value was obtained which was then related to ε(E0)(λ) and f(agg), the molar fraction of aggregated pyrenes that is wavelength independent. These experiments were conducted for three Py₁-PEO(2.5K) concentrations yielding three similar ε(E0)(λ) spectra as expected since ε(E0)(λ) is an intrinsic property of the pyrene aggregates that should not depend on pyrene concentration. The ε(E0)(λ) spectra of the pyrene aggregates of Py₁-PEO(2.5K) in water were substantially broader and red-shifted compared to that of the pyrene monomer. Its measure provides a simple means to calculate the molar fraction of aggregated pyrene units in a Py₁-PEO(2.5K) aqueous solution from the absorption of the solution. This procedure should become widely applicable to determine f(agg) of water-soluble polymers which have been hydrophobically modified with a pyrene derivative and used as models for associative polymers.
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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 | 0.001 |
| 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 | 0.001 |
| 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".