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Pyridoxal phosphate‐dependent reactions in natural products biosynthesis

2022· article· en· W4225310332 on OpenAlexaff
Katherine S. Ryan

Bibliographic record

VenueThe FASEB Journal · 2022
Typearticle
Languageen
FieldChemistry
TopicCarbohydrate Chemistry and Synthesis
Canadian institutionsUniversity of British Columbia
Fundersnot available
KeywordsEnzymeCofactorBiochemistryPyridoxal phosphateBiosynthesisChemistryPyridoxalCarbanionElectrophileStereochemistryCatalysis

Abstract

fetched live from OpenAlex

Pyridoxal 5′‐phosphate (PLP)‐dependent enzymes are widespread in nature. Most reactions catalyzed by PLP‐dependent enzymes traverse through a carbanionic intermediate, which is stabilized by the PLP cofactor. Like all enzymes that deal with carbanions, PLP‐dependent enzymes can be subject to reaction with electrophiles like O 2 . However, the majority reactions of PLP‐dependent enzymes with O 2 are paracatalytic. Recent studies have identified PLP‐dependent enzymes that employ O 2 as a co‐substrate for oxidation of arginine. Such enzymes are part of biosynthetic pathways that convert arginine into heterocycle‐containing natural products. In this talk, I will discuss the discovery of these arginine oxidases, and I will describe what we have learned about their mechanisms. I will furthermore highlight how we characterized an O 2 ‐, PLP‐dependent enzyme encoded by an unknown gene cluster and then used this discovery as a starting point to reconstitute the biosynthetic pathway to the antibiotic azomycin.

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 imitation

Not 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.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.000
Version: metacan-v3-hybrid-931329e0061cValidation status: machine_predicted_unvalidated
Candidate categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: none
Teacher disagreement score0.001
Threshold uncertainty score0.010

Distilled classifier scores by category (both heads)

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0010.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0000.001
Scholarly communication0.0010.001
Open science0.0000.000
Research integrity0.0010.002
Insufficient payload (model declined to judge)0.0010.001

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.

Opus teacher head0.014
GPT teacher head0.218
Teacher spread0.203 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it

Classification

machine, unvalidated

Machine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.

The models applied no category: nothing in the taxonomy fit this work.
Study designBench or experimental
Domainnot available
GenreEmpirical

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".

Quick stats

Citations0
Published2022
Admission routes1
Has abstractyes

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