A Density Functional Theory Investigation into the Binding of the Antioxidants Ergothioneine and Ovothiol to Copper.
Bibliographic record
Abstract
The ability of hybrid, nonhybrid and meta-GGA density functional theory (DFT) based methods (B3LYP, BP86, M06 and M06L) to provide reliable structures and thermochemical properties of biochemically important Cu(I)/(II)···ESH (ergothioneine) and ···OSH (ovothiol) has been assessed. For all functionals considered, convergence in the optimized structures and Cu(I)/(II)···S/N bond lengths is only obtained using the 6-311+G(2df,p) basis set or larger, with the nonhybrid DFT method BP86 appearing, in general, to provide the most reliable structures. The reduction potentials associated with the reduction of Cu(II) to Cu(I) when complexed with either OSH and ESH were also determined. The implications for their ability to thus help protect against Cu-mediated oxidative damage are discussed. Importantly, the binding of OSH and ESH with Cu ions disfavors Cu(I)/Cu(II) recycling by increasing the reduction potential for the Cu(II) to Cu(I) reduction and as a result, inhibits the potential oxidative damage caused by such Cu ions.
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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 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| 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) | 0.000 | 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".