Metal ion-biomolecule interactions. Part 22.<sup>1</sup> Cr(III)-catalyzed isotopic hydrogen exchange in methylimidazoles
Notice bibliographique
Résumé
The detritiation kinetics of the Cr(III) complexes 1 and 3-6 have been studied in aqueous buffers at 35°C, using the liquid scintillation counting technique. Results for 5 and 6 provide benchmark kinetic data for N-T/N-H exchange under the experimental conditions of the study and have aided in the delineation of N-T/N-H from C-T/C-H exchange in the parallel reactions observed experimentally. Curved first-order plots obtained for 1, 3, and 4 were treated to yield rate constants for two parallel exchange reactions k obs A and k obs B for the "fast" and "slow" processes, respectively. The "fast" process has been assigned to C(2)-H exchange in 1, competing N-H and C(2)-H exchange in 3, and N-H exchange in 4. In all cases, the "slow" process is associated with C(4,5)-H exchange. Identification of exchange sites in 1, 3, and 4 was made possible by the consideration of the results of an IR spectroscopic study of hydrogen-deuterium exchange, comparison of the extent of 3 H incorporatation in different complexes in the tritiation experiments, and a careful analysis of the exchange kinetic data. Analysis of the rate data indicates that Cr(III) significantly enhances C(2)-H exchange in 1 and 3, while C(4,5)-H exchange, hitherto reported in the literature only under drastic reaction conditions, was observed for 1, 3, and 4 under the mild conditions of the present study. Quantitation of the effect of Cr(III) coordination on 3 H exchange in imidazole-type nuclei was achieved fully in 1; giving k M+ values of 6 × 10 3 and 7 × 10 2 M -1 s -1 for C(2)-H and C(4,5)-H exchange, respectively. Using the literature value for k H+ , the second-order rate constant for C(2)-H exchange under H + catalysis, 2.9 × 10 2 M -1 s -1 , it follows that Cr(III) is ca. 20 times better as a catalyst for C(2)-H exchange in 1-methylimidazole than H + , providing the first example of a metal ion being more effective than a proton in these processes. Comparison of the results obtained with 1 with literature results for 2 shows a very large (ca. 3 × 10 5 -fold) difference in the catalytic activities of Cr(III) and Co(III), favouring the former. The dichotomy in the effectiveness of the two metal ions in catalyzing 3 H exchange in the imidazole nucleus has been ascribed to differences in (i) extent of M n+ N bond polarization (and the consequent effect on ligand C-H acidity); (ii) electronic configuration; (iii) crystal field stabilization and activation energies; and (iv) importance of metal-ligand π back-bonding. The study highlights the diversity of factors and complexity of interactions involved in determining the role of metal ions in biological systems, especially where such processes involve complex formation between metal ions and heterocyclic fragments of biomolecules.Key words: metal ion-biomolecule interactions, methylimidazole, isotopic hydrogen exchange, catalysis by chromium.
Récupéré en direct depuis OpenAlex et désinversé. Les résumés ne sont pas conservés dans cette base de données : les index inversés représentent 8,6 Go des 9,3 Go de texte de la base, et le serveur dispose de 13 Go libres.
Comment cette classification a été obtenuedéplier
Prédiction distillée sur la base complète
Imitation des enseignantsNi prévalence calibrée, ni vérité terrain. Validation humaine à venir. Apprise à partir de 10 348 étiquettes directes de Codex et de 10 348 étiquettes directes de Gemma. Le mode candidate est l'union des têtes enseignantes seuillées; le consensus est leur intersection. Ces sorties portent le statut machine_predicted_unvalidated et ne sont ni des étiquettes humaines ni des étiquettes directes de modèles de pointe.
Scores Codex et Gemma par catégorie
| Catégorie | Codex | Gemma |
|---|---|---|
| Métarecherche | 0,000 | 0,000 |
| Méta-épidémiologie (sens strict) | 0,000 | 0,000 |
| Méta-épidémiologie (sens large) | 0,000 | 0,000 |
| Bibliométrie | 0,000 | 0,000 |
| Études des sciences et des technologies | 0,000 | 0,000 |
| Communication savante | 0,000 | 0,000 |
| Science ouverte | 0,000 | 0,000 |
| Intégrité de la recherche | 0,000 | 0,001 |
| Charge utile insuffisante (le modèle a refusé de juger) | 0,036 | 0,000 |
Scores machine (provisoires)
Les deux têtes enseignantes du modèle étudiant, lues sur ce travail. Un score ordonne la base pour la relecture; il n'affirme jamais une catégorie, et le statut de validation accompagne chaque rangée tel quel.
Scores de référence d'un modèle non mature (critères de maturité non atteints, 7 itérations). Un score ordonne; il n'affirme jamais une catégorie.
score_only:v0-immature-baseline · tel quel depuis la passe de notation : score_only signifie que le nombre peut ordonner les travaux, et qu'aucune étiquette de catégorie n'en découleClassification
machine, non validéePrédiction automatique; un appel candidat d’une seule tête enseignante, pas un consensus.
Le détail, modèle par modèle et score par score, se trouve en fin de page sous « Comment cette classification a été obtenue ».