Dissertationen online der Freien Universität Berlin
|Haupttitel||Theoretical Investigations of Multivalent Reactions|
|Titelvariante||Theoretische Untersuchungen multivalenter Reaktionen|
|Autor||Achazi, Andreas Johannes|
Geburtsort: Berlin, Deutschland
|Gutachter||Prof. Dr. Beate Paulus|
|weitere Gutachter||Prof. Dr. Christoph A. Schalley|
|Freie Schlagwörter||DFT; Quantum Chemistry; Multivalency; Cooperativity; Crown Ether/ammonium Complexes; Samarium Diiodide; PEG|
541 Physikalische Chemie
|Zusammenfassung||A strong but easily reversible connection is important on the molecular level in biological recognition, adhesion, and signaling processes but also for drug design or supramolecular complexes. This connection can be achieved by using multivalency: the connection is formed with a large number of weak interactions instead of only one strong interaction. Multivalency and the underlying cooperative effects are not yet fully understood.|
Small multivalent crown ether/ammonium assemblies are used in this thesis as model system for multivalent interactions and as building blocks for functionalized supramolecular host-guest complexes. For analysis, a theoretical multilevel approach to determine the Gibbs energy of association in solution of these assemblies in silico has been developed. Dispersion corrected density functional theory is used to obtain the association energies in the gas phase. The effects of translation, rotation and vibration are taken into account by a rigid-rotor-harmonic-oscillator approximation with a free-rotor approximation for low-lying vibrations. The solvation is included by the implicit solvent models COSMO-RS and D-COSMO-RS. Addionally counterions have to be included explicitly for a good agreement with the experiments. The average deviation from the experimental results was about 5 kJ/mol, which is state-of-the-art.
In collaboration with specialists for supramolecular chemistry and for molecular dynamic simulations new insights into the bond formation of crown ether/ammonium assemblies and multivalency were gained. Attractive spacer-spacer interactions yield a strong positive chelate cooperativity. The results were summarized to a general guideline to create multivalent molecular assemblies with high binding affinity. Most important is a high complementarity of host and guest. A mix of preoganisation and adaptability is preferred over maximizing the preoganisation by lowering the adaptability.
Additionally this thesis includes the investigation of two functionlized supramolecular complexes: a photoswitch and a donor-acceptor complex.
The theoretical multilevel approach to determine was then applied in a mechanistic investigation of the samarium diiodide mediated reductive coupling of the N-oxoalkylsubstituted methyl indole-3-carboxylates. It was found that the high diastereoselectivity in the cyclization step is caused by the formation of an energetically highly favorable chelate complex.
Finally the stretching of polyethylene glycol in water was investigated in collaboration with experts for atomic force microscope experiments and molecular dynamic simulations. Surprisingly the stretching of polyethylene glycol in water is enthalpically unfavorable and not entropically unfavorable. This indicates that a multivalent host or guest in water with a flexible polyethylene glycol spacer suffers from an enthalpic penalty and not from an entropic penalty in complex formation. Together with the results of the crown ether/ammonium assemblies, this challenges the notion that flexible spacers cause in general an entropic penalty in complex formations. Spacer length, intramolecular interactions, solvent and counterions can affect the conformational space of both the flexible spacer and the whole system or have strong enthalpic effects. The in silico methods presented in this thesis are powerful tools to identify the important effects in chemical reactions and to comprehend the experimental findings.
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|Seitenzahl||12 ungezählte Seiten, 171 Seiten|
|Fachbereich/Einrichtung||FB Biologie, Chemie, Pharmazie|
|Tag der Disputation||27.11.2017|
|Erstellt am||04.12.2017 - 10:37:09|
|Letzte Änderung||07.12.2017 - 09:18:24|
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