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Record W4282841572 · doi:10.1021/jacs.2c04179

Source of Rate Acceleration for Carbocation Cyclization in Biomimetic Supramolecular Cages

2022· article· en· W4282841572 on OpenAlex
Q. N. Nguyen, Kay T. Xia, Yue Zhang, Nanhao Chen, Mariko Morimoto, Xiaokun Pei, Yang Ha, Jinghua Guo, Wanli Yang, Lee‐Ping Wang, Robert G. Bergman, Kenneth N. Raymond, F. Dean Toste, Dean J. Tantillo

Why this work is in the frame

A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.

fundA Canadian funder is recorded on the work.
no affNo Canadian affiliation: this work is invisible to an affiliation-only frame.
No Canadian affiliation. An affiliation-only frame, the usual design, would never have seen this work. It is one of the works that make the case for inverting the frame.

Bibliographic record

VenueJournal of the American Chemical Society · 2022
Typearticle
Languageen
FieldChemistry
TopicSupramolecular Chemistry and Complexes
Canadian institutionsnot available
FundersLawrence Berkeley National LaboratoryBasic Energy SciencesArmy Research OfficeDivision of ChemistryNatural Sciences and Engineering Research Council of CanadaU.S. Department of EnergyOffice of ScienceNational Institutes of HealthNational Science Foundation
KeywordsChemistryCarbocationSubstrate (aquarium)Supramolecular chemistryQuantum chemicalCageComputational chemistryStereochemistryGalliumMoleculeAccelerationCage effectPhotochemistryOrganic chemistry

Abstract

fetched live from OpenAlex

The results of quantum chemical and molecular dynamics calculations reveal that polyanionic gallium-based cages accelerate cyclization reactions of pentadienyl alcohols as a result of substrate cage interactions, preferential binding of reactive conformations of substrate/H3O+ pairs, and increased substrate basicity. However, the increase in basicity dominates. Experimental structure–activity relationship studies in which the metal vertices and overall charge of the cage are varied confirm the model derived via calculations.

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.

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 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: Empirical
Teacher disagreement score0.002
Threshold uncertainty score0.341

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 integrity0.0000.000
Insufficient payload (model declined to judge)0.0000.000

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 head0.011
GPT teacher head0.249
Teacher spread0.238 · 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