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Record W2084375227 · doi:10.1139/v00-020

Multidimensional conformational analysis of allyl methyl disulfide: a key component of garlic

2000· article· en· W2084375227 on OpenAlexafffundvenue
Alvin C. Lin, Salvatore J. Salpietro, Eugen Deretey, Imre G. Csizmadia

Bibliographic record

VenueCanadian Journal of Chemistry · 2000
Typearticle
Languageen
FieldAgricultural and Biological Sciences
TopicGarlic and Onion Studies
Canadian institutionsUniversity of Toronto
FundersNatural Sciences and Engineering Research Council of Canada
KeywordsChemistryDimethyl disulfideDisulfide bondAb initioConformational isomerismStereochemistryCrystallographyMoleculeSulfurOrganic chemistry

Abstract

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Organosulfur compounds in garlic, like allyl methyl disulfide, have been found to be involved in antimutagenic, anticarcinogenic, antithrombotic, and lipid-lowering activities, and it has also been found to act as an antioxidant. Ab initio molecular computations were performed on dihydrogen disulfide (1) with respect to torsional angle τ1 = τ(H·S-S·H), hydrogen methyl disulfide (2) with respect to torsional angle τ1 = τ(H·S-S·CH3), and allyl methyl disulfide (3) with respect to torsional angles τ1 = τ(H3C2·CH2·S-S·CH3), τ2 = τ(H3C2·CH2-S·S·CH3), and τ3 = τ(H3C2-CH2·S·S·CH3). Potential energy curves (PEC) were obtained from 1 and 2, i.e., E = E(τ1), from which optimized structures were obtained at the HF/6-31G* level of theory. These optimized structures were used to investigate the potential energy hypersurface surface (PEHS) of 3, i.e., E = E(τ1,τ2,τ3). One-dimensional scans along τ2 and τ3 (where τ1 = ±90°; τ1 = 180°) were performed at the HF/3-21G* level of theory. From these scans, six lower energy pairs of enantiomeric minima (i.e., [g+g+g+| g-g-g-], [g+ag- | g-ag+], [g+g-g+ | g-g+g-], [g+g+g-| g-g-g+], [g+ag- | g-ag+], and [g+g-g-| g-g+g+]) as well as 3 higher energy minima (i.e., [g+g+s | g-g-s], [g+as | g-as], and [g+g-s | g-g+s]) were optimized at τ1 = ±90° at the HF/6-31G* and B3LYP/6-31G* levels of theory. The global minimum was determined to be the [g+g-g+ | g-g+g-] enantiomeric pair of conformers, and the fully symmetrical anti-anti-anti [a a a] structure was determined to be a second-order saddle point on the PEHS of 3. Although there are no stereocentres in 3, there is chirality in the conformational twist with respect to the [a a a] conformation through τ1 = τ2 = τ3 = 180°. Based on the energies and MO diagrams of the HUMO and LUMO +1 of 3, the anticarcinogenic and cholesterol lowering activity mechanism of 3 is presented.Key words: ab initio MO computations, allyl methyl disulfide, multidimensional conformational analysis (MDCA), anticarcinogenic, cholesterol lowering.

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)0.000
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 score0.002
Threshold uncertainty score0.006

Distilled classifier scores by category (both heads)

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)0.0020.000

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 head0.013
GPT teacher head0.205
Teacher spread0.192 · 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

Citations7
Published2000
Admission routes3
Has abstractyes

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