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Record W4304776316 · doi:10.26434/chemrxiv-2022-ldq4b

Stretching Peptides

2022· preprint· en· W4304776316 on OpenAlexfundno aff
Zoë C. Adams, Anthony P. Silvestri, Sorina Chiorean, Brian P. Balo, Yifan Shi, Matthew Holcomb, Shawn I. Walsh, Colleen Maillie, Gregory K. Pierens, Stefano Forli, K. Johan Rosengren, Philip E. Dawson

Bibliographic record

VenueChemRxiv · 2022
Typepreprint
Languageen
FieldMedicine
TopicPeptidase Inhibition and Analysis
Canadian institutionsnot available
FundersNatural Sciences and Engineering Research Council of CanadaNational Institutes of HealthNational Science Foundation
KeywordsPolyproline helixTripeptideChemistryPeptideHelix (gastropod)PeptidomimeticCombinatorial chemistrySmall moleculeStereochemistryBiochemistryBiology

Abstract

fetched live from OpenAlex

Advances in the modulation of protein-protein interactions (PPIs) enable the characterization of PPI networks that govern disease mechanisms and guide the design of novel therapeutics and probes. These PPIs are often characterized by complementary binding to shallow protein surfaces that are challenging to target using standard methods for high-affinity small molecule ligand generation. Compared to linear peptides, synthetically constrained epitopes provide an energetic advantage for binding PPI surfaces by decreasing unbound-state entropy. Such peptide stapling strategies promoting α-helix and β-hairpin structures are well developed. However, approaches for accessing common extended backbone structures are limited. Here we demonstrate the incorporation of a rigid, linear, diyne brace between side chains at the i to i+2 positions to generate a family of low molecular weight peptide macrocycles adopting extended backbones. We show by NMR and DFT studies that these ‘stretched peptides’ adopt rigid and stable conformations in solution which can be tuned to explore a wide range of extended peptide conformational space, including those inherent to β-strands and polyproline II (PPII) helices. The formation of the diyne brace is accomplished in excellent conversions (>95%) and is amenable to high throughput synthesis. The minimalist structure-inducing tripeptide core (<300 Da) is amenable to further synthetic elaboration to optimize bioactivity and pharmacokinetics. We showcase the utility of diyne-braced peptides with the synthesis of macrocyclic inhibitors of bacterial signal 1 peptidase.

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)0.000
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesInsufficient payload (model declined to judge)
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Not applicable · Consensus signal: Not applicable
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.057
Threshold uncertainty score0.994

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.001
Insufficient payload (model declined to judge)0.0070.000

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.

Opus teacher head0.031
GPT teacher head0.306
Teacher spread0.275 · 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 designNot applicable
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

Citations1
Published2022
Admission routes1
Has abstractyes

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