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Record W4308593412 · doi:10.1007/s10953-022-01214-7

Predicting the Temperature Dependence of the Octanol–Air Partition Ratio: A New Model for Estimating $$\Delta {U^{ \circ}_{\text{OA}}}$$

2022· article· en· W4308593412 on OpenAlexaff
Sivani Baskaran, Akshay Podagatlapalli, Alessandro Sangion, Frank Wania

Bibliographic record

VenueJournal of Solution Chemistry · 2022
Typearticle
Languageen
FieldChemistry
TopicChemical Thermodynamics and Molecular Structure
Canadian institutionsARC Resources (Canada)The Scarborough HospitalUniversity of Toronto
FundersEuropean Chemical Industry Council
KeywordsAlgorithmPartition coefficientChemistryArtificial intelligenceComputer scienceChromatography

Abstract

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Abstract The octanol–air partition ratio ( K OA ) describes the partitioning of a chemical between air and octanol and is often used to approximate other partitioning phenomena in environmental chemistry (e.g., blood–air, atmospheric particulate matter–air, polyurethane foam-air). Such partitioning processes often occur at environmental temperatures other than 25 °C. Enthalpies $$\Delta {H^{ \circ}_{\text{OA}}}$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mrow> <mml:mi>Δ</mml:mi> <mml:msubsup> <mml:mi>H</mml:mi> <mml:mtext>OA</mml:mtext> <mml:mo>∘</mml:mo> </mml:msubsup> </mml:mrow> </mml:math> or internal energies $$\Delta {U^{ \circ}_{\text{OA}}}$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mrow> <mml:mi>Δ</mml:mi> <mml:msubsup> <mml:mi>U</mml:mi> <mml:mtext>OA</mml:mtext> <mml:mo>∘</mml:mo> </mml:msubsup> </mml:mrow> </mml:math> of phase transfer are used to express the temperature dependence of the K OA . Existing poly-parameter linear free energy relationships (ppLFERs) for predicting $$\Delta {H^{ \circ}_{\text{OA}}}$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mrow> <mml:mi>Δ</mml:mi> <mml:msubsup> <mml:mi>H</mml:mi> <mml:mtext>OA</mml:mtext> <mml:mo>∘</mml:mo> </mml:msubsup> </mml:mrow> </mml:math> were developed using a relatively small dataset. In this work we utilize a recently developed comprehensive K OA database to create and curate a $$\Delta {U^{ \circ}_{\text{OA}}}$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mrow> <mml:mi>Δ</mml:mi> <mml:msubsup> <mml:mi>U</mml:mi> <mml:mtext>OA</mml:mtext> <mml:mo>∘</mml:mo> </mml:msubsup> </mml:mrow> </mml:math> dataset containing 195 chemicals and use this dataset in the development of new predictive equations. Using the QSAR development platform QSARINS we evaluate the use of Abraham descriptors, other molecular descriptors, and the log 10 K OA at 25 °C as variables in different multilinear regression equations for $$\Delta {U^{ \circ}_{\text{OA}}}$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mrow> <mml:mi>Δ</mml:mi> <mml:msubsup> <mml:mi>U</mml:mi> <mml:mtext>OA</mml:mtext> <mml:mo>∘</mml:mo> </mml:msubsup> </mml:mrow> </mml:math> . The $$\Delta {U^{ \circ}_{\text{OA}}}$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mrow> <mml:mi>Δ</mml:mi> <mml:msubsup> <mml:mi>U</mml:mi> <mml:mtext>OA</mml:mtext> <mml:mo>∘</mml:mo> </mml:msubsup> </mml:mrow> </mml:math> of neutral organic chemicals can be reliably predicted using only the log 10 K OA (RMSE EXT = 6.86 kJ·mol −1 , $${\text{R}^{2} _{\text{adj}}}$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:msubsup> <mml:mtext>R</mml:mtext> <mml:mtext>adj</mml:mtext> <mml:mn>2</mml:mn> </mml:msubsup> </mml:math> = 0.94), only the solute’s hydrogen acidity A and the logarithm of the hexadecane–air partition ratio L (RMSE EXT = 7.23 kJ·mol −1 , $${\text{R}^{2} _{\text{adj}}}$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:msubsup> <mml:mtext>R</mml:mtext> <mml:mtext>adj</mml:mtext> <mml:mn>2</mml:mn> </mml:msubsup> </mml:math> = 0.93), or A and log 10 K OA (RMSE EXT = 6.76 kJ·mol −1 , $${\text{R}^{2} _{\text{adj}}}$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:msubsup> <mml:mtext>R</mml:mtext> <mml:mtext>adj</mml:mtext> <mml:mn>2</mml:mn> </mml:msubsup> </mml:math> = 0.95).

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: none
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.470
Threshold uncertainty score0.441

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 science0.0010.000
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 head0.011
GPT teacher head0.238
Teacher spread0.228 · 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

Citations7
Published2022
Admission routes1
Has abstractyes

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