Evidence map›Paper›PMID 41134053›Full record

ArticleJournal of the American Chemical Society2025

Establishing Selectivity Trends with Reactions of Thioesterases and Semi-Synthetic Polyketides.

Zachary C Litman, Yuanhuang Chen, David H Sherman

Abstract read
In one paragraph

Article in Journal of the American Chemical Society, 2025. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Not yet cited in PubMed.

0numbers the graph read from it
0cells of the map it votes in
0citing papers in PubMed
–field-weighted citation impact
1 · What the graph read from it

What it found

Each row is one number read from the abstract, on the scale the paper reported it, with its interval. Left of the dashed line favours the treatment, right favours the comparator. Under each row is the sentence it came from. New to these charts? A ten-minute tutorial.

The abstract states no effect estimate the extractor could read, or names no intervention and outcome on the map, so this paper lights no cell and moves no belief. It is still indexed, cited and linked below.

2 · The registry

The trial behind it

Trials whose registry record cites this paper, or whose number appears in the abstract. A trial that started after this paper was published is citing it as background, not reporting it.

Neither the registry nor the abstract names a trial number. If this is a trial report, that itself is worth knowing.

3 · Its place in the literature

Who cites it

0 citing papers in PubMed.

No citing paper in PubMed yet.

4 · The record

Corrections and comments

PubMed lists nothing against this paper. Absence here is not a guarantee, only a check that was made.

5 · Who and what money

Authors and funding

3 authors.

Zachary C LitmanUniversity of Michigan, Life Sciences Institute, Ann Arbor, Michigan 48109, United States.ORCID 0000-0001-5573-2805
Yuanhuang ChenUniversity of Michigan, Life Sciences Institute, Ann Arbor, Michigan 48109, United States.ORCID 0000-0001-7404-5170
David H ShermanUniversity of Michigan, Life Sciences Institute, Ann Arbor, Michigan 48109, United States.ORCID 0000-0001-8334-3647

Funding

TRAINING IN MOLECULAR AND CELLULAR CARDIOLOGYT32HL007853 · NHLBI · UNIVERSITY OF MICHIGAN AT ANN ARBOR · PI David J. Pinsky · 1996 to 2026
$11.6M
Discovery and Characterization of Natural Product Systems-Research Supplement to Promote DiversityR35GM118101 · NIGMS · UNIVERSITY OF MICHIGAN AT ANN ARBOR · PI SHERMAN, DAVID H · 2016 to 2025
$3.3M
Engineering Thioesterases for the Selective Synthesis of MacrolidesF32GM137465 · NIGMS · UNIVERSITY OF MICHIGAN AT ANN ARBOR · PI LITMAN, ZACHARY CHARLES · 2020 to 2020
$65k
NHLBI NIH HHS T32 HL007853NIGMS NIH HHS F32 GM137465NIGMS NIH HHS R35 GM118101
6 · The paper itself

Abstract

Polyketides are a diverse class of natural products with a wide range of therapeutic properties. They have been widely used in clinical settings as antibiotics, antifungals, anticancer agents, and immunosuppressants. A major subset of these molecules is produced by type I assembly line polyketide synthases (T1ALPKSs), large enzyme complexes that catalyze their stepwise construction. Understanding the selectivity and scope of T1ALPKS domains could greatly expand the diversity of products generated by these synthases and their components. This study explores the reactivity and selectivity of the terminal domains of T1ALPKSs, known as thioesterases (TEs). A panel of 25 wild-type and 10 mutant (Ser→Cys) thioesterases was reacted with semisynthetic substrates. The selectivity with which these TEs form 12- and/or 14-membered macrolactones and one or both of a pair of diastereomeric 14-membered macrolactones was quantified. The results indicate that the selectivity with which wild-type TEs react with unnatural substrates correlates with their parent T1ALPKSs, enabling the assignment of TEs into groups. Additionally, our experiments reveal that mutant (Ser→Cys) TEs often have expanded scopes compared to their wild-type counterparts and that some wild-type TEs are capable of hydrolyzing macrolactones. We demonstrated the synthetic applications of TEs with kinetic resolutions and preparative-scale reactions. This study provides a framework for organizing TEs and predicting their reactivity and selectivity, facilitating future research on structure-activity relationships and supporting directed evolution studies.

Indexed as

PolyketidesPolyketide SynthasesThiolester HydrolasesSubstrate SpecificityPolyketidesPolyketide SynthasesThiolester Hydrolases

Identifiers

PMID41134053
PMCPMC13045740

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Registered trials

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Read under generation 80e0d062 · epoch 390. Bibliography from PubMed, PubMed Central and OpenAlex; grants from NIH RePORTER; trial links from ClinicalTrials.gov; estimates, votes and beliefs from the OpenQuestion graph.