Confusing Ions on Purpose: How Many Parent Acid Molecules Can Be Incorporated in a Herbicidal Ionic Liquid?
Bibliographic record
Abstract
To expand the application range of herbicidal ionic liquids (HILs), we attempted to increase the amount of the systemic herbicide dicamba in its HILs through the formation of neither purely ionic nor neutral hydrogen-bonded complexes (so-called oligomeric ions) of parent acid and conjugate base. We realized we faced an important question—how far is it possible to increase the amount of active species (thus reducing chemical burden and extra cost) while still retaining the favorable properties of an IL? To answer this question, we prepared and characterized a range of dicamba salts with the cations tetrabutylphosphonium ([P 4444 ] + ), betainium ([HBet] + ), and carnitinium ([HCar] + ) with varying stoichiometries of excess dicamba acid (HDic). Reactions of [P 4444 ][OH] or zwitterionic betaine (Bet) or carnitine (Car) with methanolic solutions of HDic in 1:1, 1:2, 1:3, 1:4, and 1:5 stoichiometries led, after solvent removal, to the salts [Cat][H n –1 (Dic) n ] ([Cat] = [P 4444 ] +, [HBet] +, [HCar] +; n = 1–4). At 1:1 stoichiometry, the known low melting salts, [P 4444 ][Dic], [HBet][Dic], and [HCar][Dic], were isolated, of which [P 4444 ][Dic] can be classified as an IL. All salts with up to a 3-fold excess HDic, except [P 4444 ][H(Dic) 2 ], were liquid at room temperature when initially prepared, although [HBet][H(Dic) 2 ] crystallized on standing over a period of 8 weeks. Single-crystal X-ray diffraction, 1 H NMR, and Fourier transform infrared spectroscopy revealed that the degree of proton transfer or sharing was dependent on the cation, with phosphonium salts being fully ionic, carnitinium salts being less ionized and retaining some of carnitine’s zwitterionic character, and betainium salts sharing protons equally at the 1:1 composition. The results also indicate that the limit of HDic that can be accommodated in these formulations is a 1:4 M ratio since all reactions at 1:5 stoichiometry precipitated HDic upon standing.
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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 | 0.001 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.001 | 0.003 |
| Open science | 0.001 | 0.002 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 0.002 |
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".