Understanding of the Nucleation Induced Cooperative Behavior in Complex Macromolecular Systems
Digital Document
Document
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http://hdl.handle.net/11134/20002:860653841
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Persons
Creator (cre): Fu, Hailin
Major Advisor (mja): Lin, Yao
Associate Advisor (asa): Kasi, Rajeswari
Associate Advisor (asa): Nieh, Mu-Ping
Associate Advisor (asa): Papadimitrakopoulos, Fotios
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Title |
Title
Title
Understanding of the Nucleation Induced Cooperative Behavior in Complex Macromolecular Systems
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Origin Information
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Parent Item
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Digital Origin |
Digital Origin
born digital
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Description |
Description
Cooperativity is seen in enzymes and receptors which describes that the binding affinity in one binding event can be affected by the previous binding event on the same protein. The cooperative behavior is also widely found in the macromolecular system, say the coil to helix transition of polypeptides and the supramolecular self-assembly of proteins and synthetic molecules. Theoretical models concerning the coil to helix transition of polypeptides and the cooperative supramolecular polymerization are well developed. In particular, various kinetic models for supramolecular polymerization based on homogeneous nucleation and heterogeneous nucleation have been developed since the discovery of the cooperative assembly behavior in actin polymerization by Oosawa about 50 years ago. In contrast, there is no systematic investigation on the kinetic modelling of cooperative covalent polymerization. The reason might be that the study of the cooperative behavior in covalent polymerization is still in the nascent stage. Herein, we’ll first focus on using the traditional homogeneous and heterogeneous nucleation controlled growth model to analyze the kinetic behavior of a complex supramolecular self-assembly system coupled with a chemical reaction. For the rest, we’ll focus on the establishment of new kinetic models for the cooperative covalent polymerization of N-carboxyanhydrides (NCA) we recently found. An irreversible kinetic model was first adapted from the homogeneous nucleation induced growth model and was found to be able to correctly account for the two-stage kinetic curves. But to correctly account for both the kinetic curves and the molecular weight distribution, a reversible binding process of the monomers (Michaelis-Menten kinetics) need to be incorporated into the first model. Then a series of kinetic models with competing pathways were designed to address the competing reactions of NCA with various initiators in emulsion polymerization. Lastly, we examined the assumptions of fixed nucleus size and equal reactivity by treating the coil-helix transition with the zipper model and proposing one possible way of treating decaying rate constant.
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Organizations
Degree granting institution (dgg): University of Connecticut
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Rights Statement
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Use and Reproduction |
Use and Reproduction
These materials are provided for educational and research purposes only.
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Note
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Local Identifier |
Local Identifier
OC_d_1997
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