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The Di‐Iron Oxygenase<scp>PhnZ</scp>

2016· other· en· W3194955520 on OpenAlexaff
Jacqueline P. Séguin, David L. Zechel

Bibliographic record

VenueEncyclopedia of Inorganic and Bioinorganic Chemistry · 2016
Typeother
Languageen
FieldChemistry
TopicMetal-Catalyzed Oxygenation Mechanisms
Canadian institutionsQueen's University
Fundersnot available
KeywordsDioxygenaseChemistryActive siteStereochemistryBinding siteEnzymeCofactorBiochemistry

Abstract

fetched live from OpenAlex

Abstract PhnZ is a di‐iron‐dependent monooxygenase from the HD superfamily of metal ion‐dependent phosphohydrolases. These enzymes utilize a conserved histidine‐aspartate motif in the active site for metal ion binding. PhnZ is commonly found in marine bacteria where it works in tandem with the α‐ketoglutarate‐dependent dioxygenase PhnY to extract inorganic phosphate from the organophosphonate natural product 2‐aminoethylphosphonic acid. PhnY hydroxylates 2‐aminoethylphosphonic acid stereospecifically to generate ( R )‐2‐amino‐1‐hydroxyethylphosphonic acid, whereupon PhnZ catalyzes the oxidative cleavage of the carbon–phosphorus bond yielding glycine and inorganic phosphate. Analysis of the metal ion dependence of PhnZ through activity assays, ICP‐MS, Mössbauer spectroscopy, and EPR spectroscopy have shown that this enzyme utilizes a mixed‐valence Fe(II)/Fe(III) di‐iron cofactor for catalysis. The X‐ray crystal structures of PhnZ have revealed that one Fe ion (Fe2) is used to bind the substrate in a bidentate manner, while the other Fe ion (Fe1) is likely used to reduce dioxygen. Two conserved active site residues, Y24 and E27, are observed to migrate in and out of the active site in response to substrate binding. Y24 is observed to bind Fe2, occupying the putative dioxygen binding site, but is expelled upon recognition of the substrate amino group by the residue E27. This is proposed to allow dioxygen to bind to Fe1, placing it well within proximity of the substrate bound at Fe2. A mechanism for oxidative carbon–phosphorus bond cleavage by PhnZ has been proposed based on these results. PhnZ not only represents the third known mechanism for enzymatic cleavage of CP‐bonds but also provides a window into the evolution of new functions within an enzyme superfamily.

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 distilled prediction

Teacher imitation

Not 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.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.001
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesMeta-epidemiology (narrow), Insufficient payload (model declined to judge)
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: none
GenreCandidate signal: Other · Consensus signal: Other
Teacher disagreement score0.289
Threshold uncertainty score1.000

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.001
Meta-epidemiology (narrow)0.0010.001
Meta-epidemiology (broad)0.0010.000
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0010.001
Research integrity0.0010.001
Insufficient payload (model declined to judge)0.0160.001

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 head0.005
GPT teacher head0.205
Teacher spread0.201 · 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 teacher head, not a consensus.

Study designBench or experimental
Domainnot available
GenreOther

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
Published2016
Admission routes1
Has abstractyes

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