Trends in Hydrophilicity/Lipophilicity of Phosphonium Ionic Liquids As Determined by Ion-Transfer Electrochemistry
Bibliographic record
Abstract
Ionic liquids (ILs) have become valuable new materials for a broad spectrum of applications including additives or components for new hydrophobic/hydrophilic polymer coatings. However, fundamental information surrounding IL molecular properties is still lacking. With this in mind, the microinterface between two immiscible electrolytic solutions (micro-ITIES), for example, water|1,2-dichloroethane, has been used to evaluate the hydrophobicity/lipophilicity of 10 alkylphosphonium ILs. By varying the architecture around the phosphonium core, chemical differences were induced, changing the lipophilicity/hydrophilicity of the cations. Ion transfer (IT) within the polarizable potential window (PPW) was measured to establish a structure-property relationship. The Gibbs free energy of IT and the solubility of their ILs were also calculated. For phosphonium cations bearing either three butyl or three hydroxypropyl groups with a tunable fourth arm, the latter displayed a wide variety of easily characterizable IT potentials. The tributylphosphonium ILs, however, were too hydrophobic to undergo IT within the PPW. Utilizing a micro-ITIES (25 μm diameter) housed at the tip of a capillary in a uniquely designed pipet holder, we were able to probe beyond the traditional potential window and observe ion transfer of these hydrophobic phosphonium ILs for the first time. A similar trend in lipophilicity was determined between the two subsets of ILs by means of derived solubility product constants. The above results serve as evidence of the validation of this technique for the evaluation of hydrophobic cations that appear beyond the conventional PPW and of the lipophilicity of their ILs.
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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 | 0.001 |
| 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".