Synthesis of Isotopically Labelled Disparlure Enantiomers and Application to the Study of Enantiomer Discrimination in Gypsy Moth Pheromone‐Binding Proteins
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Bibliographic record
Abstract
To study the binding mechanism of disparlure (7,8)‐epoxy‐2‐methyloctadecane enantiomers with pheromone‐binding proteins (PBPs) of the gypsy moth, oxygen‐17 or 18 and 5,5,6,6‐deuterium labelled disparlure enantiomers were prepared in an efficient, enantioselective route. Key steps involve the asymmetric α‐chlorination of dodecanal by SOMO catalysis and Mitsunobu inversion of a 1,2‐chlorohydrin. The pheromone, (+)‐disparlure (7 R , 8 S ), was tested in two infested zones, demonstrating that it is very attractive towards male gypsy moths. Studies of the binding of (+)‐disparlure and its antipode to gypsy moth PBPs by 2 H & 17 O NMR at 600 MHz are reported. Chemical shifts, spin‐lattice relaxation decay times (T 1 ) and transverse relaxation decay times (T 2 ) of deuterium atoms of disparlure enantiomers in 2 H NMR show that the binding of disparlure enantiomers to PBP1 differs from binding to PBP2, as expected from their opposite binding preferences (PBP1 binds (–)‐disparlure, and PBP2 binds (+)‐disparlure more strongly). Models of the disparlure enantiomers bound to one internal binding site and two external binding sites of both PBPs were constructed. The observed chemical shift changes of deuterated ligand signals, from non‐bound to bound, T 1 and T 2 values are correlated with results from the simulations. Together these results suggest that the disparlure enantiomers adopt distinct conformations within the binding sites of the two PBPs and interact with residues that line the sites.
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Full frame distilled prediction
Teacher imitationNot 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.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.001 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
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.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it