Scission of Glucosidic Bonds by a Lentinus similis Lytic Polysaccharide Monooxygenases Is Strictly Dependent on H<sub>2</sub>O<sub>2</sub>while the Oxidation of Saccharide Products Depends on O<sub>2</sub>
Bibliographic record
Abstract
Lytic polysaccharide monooxygenases (LPMOs) are mononuclear copper enzymes that act in synergy with glycoside hydrolases to saccharify the most abundant polysaccharides in nature. Both O 2 and H 2 O 2 can be cosubstrates for LPMOs. The Lentinus similis LPMO (LsAA9A) has previously been shown to oxidatively cleave oligosaccharides when supplied with ascorbate as a reductant. This study demonstrates that LsAA9A is unable to complete the catalytic cycle and cleave cellulose without H 2 O 2 . Instead, cellooligomers efficiently prevent the slow continuous oxidation of ascorbate taking place under ambient conditions in the absence of a substrate. LsAA9A specifically cleaves cellooligomers in a fast and stoichiometric reaction with H 2 O 2 as a cosubstrate. However, the product profile contains more non-oxidized saccharides than anticipated by the generally accepted LPMO reaction scheme. The scission of glucosidic bonds and oxidation of the saccharide therefore appear not to be directly coupled. This was confirmed by the complete absence of oxidized products under anoxic conditions. A mechanism is proposed involving the hydrolysis of a cellulosic radical formed by a H 2 O 2 -derived caged hydroxyl radical. In addition, LsAA9A catalyzes another stoichiometric reaction with excess H 2 O 2 to oxidize ascorbate in the absence of cellulose. Ascorbate is not a cosubstrate for the reaction leading to the scission of glucosidic bonds by LsAA9A.
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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 | 0.000 |
| 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) | 0.001 | 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 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".