Hydrolysis of polyhydroxy polyunsaturated fatty acid<scp>‐</scp>glycerophosphocholines by Group <scp>IIA</scp>, V, and X secretory phospholipases <scp>A<sub>2</sub></scp>
Bibliographic record
Abstract
Abstract It is widely accepted that unesterified polyunsaturated ω‐6 and ω‐3 fatty acids (PUFA) are converted through various lipoxygenases, cyclooxygenases, and cytochrome P450 enzymes to a range of oxygenated derivatives (oxylipins), among which the polyhydroxides of unesterified PUFA have recently been recognized as cell signaling molecules with anti‐inflammatory and pro‐resolving properties, known as specialized pro‐resolving mediators (SPMs). This study investigates the mono‐, di‐, and trihydroxy 16:0/PUFA‐GPCs, and the corresponding 16:0/SPM‐GPC, in plasma lipoproteins. We describe the isolation and identification of mono‐, di‐, and trihydroxy AA, EPA, and DHA‐GPC in plasma LDL, HDL, HDL3, and acute phase HDL using normal phase LC/ESI‐MS, as previously reported. The lipoproteins contained variable amounts of the polyhydroxy‐PUFA‐GPC (0–10 nmol/mg protein), likely the product of lipid peroxidation and the action of various lipoxygenases and cytochrome P450 enzymes on both free fatty acids and the parent GPCs. Polyhydroxy‐PUFA‐GPC was hydrolyzed to variable extent (20%–80%) by the different secretory phospholipases A 2 ( sPLA 2 s), with Group IIA sPLA 2 showing the lowest and Group X sPLA 2 the highest activity. Surprisingly, the trihydroxy‐16:0/PUFA‐GPC of APHDL was largely absent, while large amounts of unidentified material had migrated in the free fatty acid elution area. The free fatty acid mass spectra were consistent with that anticipated for branched chain polyhydroxy fatty acids. There was general agreement between the masses determined by LC/ESI‐MS for the polyhydroxy PUFA‐GPC and the masses calculated for the GPC equivalents of resolvins, protectins, and maresins using the fatty acid structures reported in the literature.
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How this classification was reachedexpand
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 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.001 | 0.001 |
| 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 teacher head, 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".