Dendrimeric and polymeric rotaxanes incorporating the Loeb recognition motif.
Notice bibliographique
Résumé
Traditionally, dendrimeric and polymeric macromolecules have been pieced together using the strength of covalent and metal coordinative bonds. The incorporation of non-covalent interactions within these polymers may prove interesting in the fundamental role that interlocked components play in entanglements, rheology, elasticity and mechanical properties of the polymers in which they will be incorporated. The focus of this thesis is to explore the incorporation of the 1,2-bis(pyridinium)ethane (Loeb) rotaxane motif into various polymeric and dendrimeric architectures and study how these new interpenetrated and interlocked components affect the properties of the resulting systems. A series of molecules possessing both recognition elements covalently bound to one another, in a daisy chain fashion, were synthesized in order to study their self-complexing and oligomerizing abilities in competitive and non-competitive solvents. Proton nuclear magnetic resonance (1 H NMR) spectroscopy and high resolution electrospray ionization mass spectrometry (ESI-MS) were used to characterize these compounds and study their polymerization behavior. The same rotaxane motif was then used to synthesize a series of branched [n]rotaxanes. [2]-, [3]- and [4]Rotaxanes were obtained using a threading followed by stoppering approach and subsequently characterized by 1H NMR spectroscopy and ESI-MS. Isolated product yields and product distributions are discussed with respect to the core size and macrocyclic arrangement about the core. To study the effect of incorporating Frechet dendrons as stoppers and as macrocyclic appendages into this rotaxane motif, various dendrimeric [2]rotaxanes were synthesized. By altering the size of the dendrons employed, a 1H NMR spectroscopic study was performed in a variety of solvents of differing polarity. Their results as well as ESI-MS investigations will be discussed. Finally, Frechet dendrons were incorporated into a series of [3]rotaxanes and their [2]rotaxane molecular shuttle counterparts. This was done in order to study the effect dendrons have on the translational isomerism of shuttling [2]rotaxane systems. The systems were characterized by 1H NMR spectroscopy and ESI-MS. In addition, the rates of the shuttling process as well as the recognition site occupancy were measured using variable temperature NMR (VT-NMR) spectroscopy as well as NMR simulation software. These final results will be presented.Dept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis2005 .T73. Source: Dissertation Abstracts International, Volume: 66-11, Section: B, page: 5990. Thesis (Ph.D.)--University of Windsor (Canada), 2005.
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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 | 0,001 | 0,000 |
| Communication savante | 0,000 | 0,000 |
| Science ouverte | 0,000 | 0,000 |
| Intégrité de la recherche | 0,000 | 0,000 |
| Charge utile insuffisante (le modèle a refusé de juger) | 0,002 | 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 ».