A Computational Investigation of the Binding of the Selenium Analogues of Ergothioneine and Ovothiol to Cu(I) and Cu(II) and the Effect of Binding on the Redox Potential of the Cu(II)/Cu(I) Redox Couple
Bibliographic record
Abstract
The complexes formed from the binding of ovoselenol (OSeH) and ergoseloneine (ESeH) to Cu(II) and Cu(I) have been investigated with DFT methods. From the calculated thermodynamics, the binding of OSeH and ESeH to Cu(II) and Cu(I) ions increases the reduction potential for the Cu(II)/Cu(I) redox couple. The calculated reduction potentials for the Cu(II)(OSe)2/Cu(I)(OSeH)3+ and Cu(II)(ESe)2/Cu(I)(ESeH)3+ redox couples were found to be 1.15 V and 1.24 V in a dilute aqueous solution. By combining the half reactions for the oxidation of OSeH to the diselenide OSeSeO with the reduction of Cu(II)(OSe)2 to Cu(I)(OSeH)3+, the calculated EMF was 0.90 V. For the oxidation of ESeH to the diselenide ESeSeE with the concomitant reduction of Cu(II)(ESe)2 to Cu(I)(ESeH)3+, the calculated EMF was 0.67 V. Thus, for both systems, the reduction of Cu(II) to Cu(I) with concomitant formation of either diselenide is thermodynamically favourable, and it is expected that both OSeH and ESeH are suitable for the protection against copper induced oxidative damage. As a result, the inhibition of the recycling of Cu(I) to Cu(II) is thermodynamically favourable in the presence of OSeH and ESeH.
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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 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.002 | 0.001 |
| Bibliometrics | 0.001 | 0.001 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.002 | 0.001 |
| Research integrity | 0.002 | 0.001 |
| Insufficient payload (model declined to judge) | 0.008 | 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".