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Record W2332050257 · doi:10.1021/ac4033615

“Retention Projection” Enables Reliable Use of Shared Gas Chromatographic Retention Data Across Laboratories, Instruments, and Methods

2013· article· en· W2332050257 on OpenAlexfundno aff
Brian B. Barnes, Michael B. Wilson, Peter W. Carr, Mark F. Vitha, Corey D. Broeckling, Adam L. Heuberger, Jessica E. Prenni, Gregory C. Janis, Henry Corcoran, Nicholas H. Snow, Shilpi Chopra, Ramkumar Dhandapani, Amanda Tawfall, Lloyd W. Sumner, Paul G. Boswell

Bibliographic record

VenueAnalytical Chemistry · 2013
Typearticle
Languageen
FieldChemistry
TopicAnalytical Chemistry and Chromatography
Canadian institutionsnot available
FundersNational Institute of General Medical SciencesNational Institutes of HealthWorld Anti-Doping Agency
KeywordsKovats retention indexChemistryRetention timeChromatographyData retentionTwo-dimensional gasReliability (semiconductor)Mass spectrometryGas chromatographyProjection (relational algebra)Analytical Chemistry (journal)AlgorithmComputer sciencePower (physics)

Abstract

fetched live from OpenAlex

Gas chromatography/mass spectrometry (GC/MS) is a primary tool used to identify compounds in complex samples. Both mass spectra and GC retention times are matched to those of standards; however, it is often impractical to have standards on hand for every compound of interest, so we must rely on shared databases of MS data and GC retention information. Unfortunately, retention databases (e.g., linear retention index libraries) are experimentally restrictive, notoriously unreliable, and strongly instrument dependent, relegating GC retention information to a minor, often negligible role in compound identification despite its potential power. A new methodology called "retention projection" has great potential to overcome the limitations of shared chromatographic databases. In this work, we tested the reliability of the methodology in five independent laboratories. We found that, even when each lab ran nominally the same method, the methodology was 3-fold more accurate than retention indexing because it properly accounted for unintentional differences between the GC/MS systems. When the laboratories used different methods of their own choosing, retention projections were 4- to 165-fold more accurate. More importantly, the distribution of error in the retention projections was predictable across different methods and laboratories, thus enabling automatic calculation of retention time tolerance windows. Tolerance windows at 99% confidence were generally narrower than those widely used even when physical standards are on hand to measure their retention. With its high accuracy and reliability, the new retention projection methodology makes GC retention a reliable, precise tool for compound identification, even when standards are not available to the user.

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: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.083
Threshold uncertainty score1.000

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.001
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0010.000
Bibliometrics0.0000.001
Science and technology studies0.0000.001
Scholarly communication0.0000.001
Open science0.0010.001
Research integrity0.0010.000
Insufficient payload (model declined to judge)0.0030.000

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 head0.050
GPT teacher head0.319
Teacher spread0.270 · 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
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
Published2013
Admission routes1
Has abstractyes

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