Capture and identification of the electrogenerated picosecond intermediates by mass spectrometry
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Bibliographic record
Abstract
Probing and identification of the reactive intermediates in electrochemical transformations is essential for gaining in-depth insights into their reaction mechanisms. However, due to their extremely short lifetimes, characterizing the electrogenerated transient species remains a significant challenge for currently available techniques. In this work, we report the first mass spectrometric identification of the electrogenerated transient nitrenium ions (R2N+) and oxenium ions (R–O+), whose lifetimes in solutions are as short as picoseconds. This achievement is made possible by the fabrication of a dual-function hybrid ultramicroelectrode/ion emitter, which permits the in-situ generation and rapid transferring of the fleeting intermediates into the gas phase for mass spectrometric analysis. For the first time, a series of previously hypothetical nitrenium/oxenium ions, including the long-sought glycosyl cations, were directly probed using mass spectrometry. Additionally, we also propose a viable mechanism involving the stabilizing effects of the positively charged microdroplets to explain the capture of the transient intermediates.
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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 | 0.001 |
| 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) | 0.001 | 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 it