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Record W2740919624 · doi:10.1021/jacs.7b05116

Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy

2017· article· en· W2740919624 on OpenAlexafffund
Eileen Yu Sneeden, Mark J. Hackett, Julien J. H. Cotelesage, Roger C. Prince, Monica Barney, Kei Goto, Eric Block, Ingrid J. Pickering, Graham N. George

Bibliographic record

VenueJournal of the American Chemical Society · 2017
Typearticle
Languageen
FieldPhysics and Astronomy
TopicAdvanced Chemical Physics Studies
Canadian institutionsUniversity of Saskatchewan
FundersSLAC National Accelerator LaboratoryBiological and Environmental ResearchNational Institute of General Medical SciencesBasic Energy SciencesNatural Sciences and Engineering Research Council of CanadaDivision of ChemistryStockholms UniversitetOffice of ScienceNational Institutes of HealthCanada Research ChairsNational Science FoundationCanadian Institutes of Health ResearchSaskatchewan Health Research FoundationUniversity of La VerneUniversity of SaskatchewanHeart and Stroke Foundation of CanadaU.S. Department of Energy
KeywordsChemistryRadicalSulfurAbsorption spectroscopyPhotochemistrySpectroscopyAbsorption (acoustics)Spectral lineIrradiationX-ray absorption spectroscopyK-edgeAbsorption edgeX-rayOrganic chemistryOpticsBand gap

Abstract

fetched live from OpenAlex

Sulfur-based thiyl radicals are known to be involved in a wide range of chemical and biological processes, but they are often highly reactive, which makes them difficult to observe directly. We report herein X-ray absorption spectra and analysis that support the direct observation of two different thiyl species generated photochemically by X-ray irradiation. The thiyl radical sulfur K-edge X-ray absorption spectra of both species are characterized by a uniquely low energy transition at about 2465 eV, which occurs at a lower energy than any previously observed feature at the sulfur K-edge and corresponds to a 1s→3p transition to the singly occupied molecular orbital of the free radical. Our results constitute the first observation of substantial levels of thiyl radicals generated by X-ray irradiation and detected by sulfur K-edge X-ray absorption spectroscopy.

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 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 score0.070
Threshold uncertainty score0.740

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0010.001
Bibliometrics0.0000.000
Science and technology studies0.0000.001
Scholarly communication0.0000.000
Open science0.0020.000
Research integrity0.0000.001
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 head0.014
GPT teacher head0.267
Teacher spread0.253 · 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.

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

Citations24
Published2017
Admission routes2
Has abstractyes

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