Cholesterol Autoxidation Revisited: Debunking the Dogma Associated with the Most Vilified of Lipids
Bibliographic record
Abstract
The longstanding dogma that cholesterol (chol) autoxidation gives chol 7-hydroperoxide (7-OOH) as the sole primary product is shown to be invalid. In fact, the epimers of each of chol 4-OOH, 6-OOH, and 7-OOH are readily formed. Although the C4-H bond that must be cleaved to produce the chol 4-OOH and 6-OOH products is significantly stronger than the C7-H bond, H-atom abstraction from C4 is facilitated by H-bond formation between the attacking peroxyl radical and the 3β-OH. Chol 5α-OOH is also formed, but only in the presence of a good H-atom donor. Chol 5α-OOH and 6-OOH undergo Hock fragmentation to yield the secosterols implicated in cardiovascular and neurodegenerative diseases, suggesting that they are likely to arise simply from autoxidation and not from reactions with O3 or (1)O2.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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 | 0.009 | 0.008 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.002 | 0.001 |
| Science and technology studies | 0.002 | 0.020 |
| Scholarly communication | 0.005 | 0.019 |
| Open science | 0.002 | 0.004 |
| Research integrity | 0.008 | 0.021 |
| Insufficient payload (model declined to judge) | 0.002 | 0.001 |
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".