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Record W4404542268 · doi:10.26434/chemrxiv-2024-66xzb

Comparison of PGSE NMR and ESI-MS Measurements on Methylaluminoxane

2024· preprint· en· W4404542268 on OpenAlexaff
Luca Rocchigiani, Scott Collins, J. Scott McIndoe, Mikko Linnolahti

Bibliographic record

VenueChemRxiv · 2024
Typepreprint
Languageen
FieldChemistry
TopicAnalytical Chemistry and Chromatography
Canadian institutionsUniversity of Victoria
FundersAcademy of Finland
KeywordsChlorobenzeneChemistryMolar massTolueneDispersitySolventMolar mass distributionNuclear magnetic resonance spectroscopyProton NMRAnalytical Chemistry (journal)Physical chemistryCatalysisOrganic chemistryPolymer

Abstract

fetched live from OpenAlex

PGSE NMR and ESI-MS studies of different grades of hydrolytic MAO demonstrate that the average dimensions and anion distribution of MAO are correlated with one another, as revealed through studies of aging and gelation of a commercial formulation of MAO. Formulations featuring an anion distribution skewed to higher m/z ratios have significantly higher activator contents as measured by 1H NMR spectroscopy in otherwise very similar formulations. PSGE NMR studies in toluene vs. chlorobenzene media demonstrate that the average dimensions of MAO are largely unaffected by solvent polarity, though aggregation behavior is more pronounced in the more polar solvent. As for catalyst activation and ion-pair speciation, the situation in polar solvents is complicated by the formation of solvated cations (and anions) in chlorobenzene which dramatically lower dimensions. DFT studies of model aluminoxane structures in the size range for MAO featuring a variety of architectures, molar mass and Me3Al content reveal that a linear correlation between Dt, as measured by PGSE NMR, can be related to molar mass using simple relationships and estimates of molecular volume if suitable high molecular weight standards are available. There is a reasonable agreement in molar mass with available ESI-MS data, recognizing that MAO is not monodisperse.

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 machine prediction

Teacher imitation

Not calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.001
Version: metacan-v3-hybrid-931329e0061cValidation 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 score0.004
Threshold uncertainty score0.012

Distilled classifier scores by category (both heads)

CategoryCodexGemma
Metaresearch0.0000.001
Meta-epidemiology (narrow)0.0010.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0010.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.001
Insufficient payload (model declined to judge)0.0040.001

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 head0.070
GPT teacher head0.331
Teacher spread0.261 · 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 source (direct Gemma or distilled Codex), 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

Citations0
Published2024
Admission routes1
Has abstractyes

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