Luminescence Quenching of Dyes by Oxygen in Core−Shell Soft-Sphere Ionic Liquids
Bibliographic record
Abstract
We examined the photoluminescence and susceptibility to quenching by atmospheric oxygen of a series of phosphorescent dyes dissolved in a core−shell “soft-sphere” ionic liquid matrix consisting of a 7 nm diameter silica core surrounded by a mobile phase consisting of end-grafted flexible chains. While this medium is macroscopically uniform in composition, it is locally heterogeneous on the nanometer length scale. Luminescent dyes provide an opportunity for assessing some of the properties of this local heterogeneity. The PL decay profiles of both platinum ocatethyl porphine (PtOEP) and [Ru(dpp) 3 ]Cl 2 could be fitted to a simple exponential form over a range of partial oxygen pressures. Taking the behavior of PtOEP as “normal,” we calculate an oxygen permeability in the liquid of P O 2 = 4 × 10 - 12 mol cm - 1 s - 1 atm - 1, comparable to that of poly( n -butyl thionylphosphazene) (C 4 PATP) but smaller than that (18 ± 2 × 10 - 12 mol cm - 1 s - 1 atm - 1 for poly(dimethylsiloxane) (PDMS). The smaller slope of the Stern−Volmer quenching plot for [Ru(dpp) 3 ]Cl 2 could be rationalized in terms of two factors, the known smaller cross section for quenching by oxygen for this dye coupled with the likelihood that this dye is located in a more rigid ionic environment characterized by a somewhat smaller local diffusion coefficent for oxygen.
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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) | 0.000 | 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 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".