Skip to Main Content
 

Global Search Box

 
 
 
 

ETD Abstract Container

Abstract Header

Hierarchical Supramolecular Structures based on Molecular Nanoparticles from Bulk to Thin Film State

Hsu, Chih-Hao

Abstract Details

2014, Doctor of Philosophy, University of Akron, Polymer Science.
Molecular nanoparticles (MNPs), such as [60]fullerene (C60), polyhedral oligomeric silsesquioxane (POSS), and polyoxometalate (POM), are nano-objects possessing shape- and volume-persistency and precisely defined molecular structure with specific symmetry. Because of their inherent physical properties and the feasible functionalization, MNPs have been considered as a unique class of building blocks for nanomaterials to bridge the molecular functionalities and material properties across different length scales through supramolecular hierarchical structures. The well-developed “click chemistry” in our group facilitates a diverse molecular design of “giant molecules” consisted of MNPs as building blocks, such as giant shape amphiphiles, giant polyhedron, and giant surfactants. The purpose of this research is to study the formation of hierarchical structures and transition behaviors of giant molecules in bulk and thin film states to reveal the structure formation mechanisms and to further build up the understanding of dependencies of the molecular architectures, topologies, and volume fraction of building blocks on the self-assembled supramolecular structures. The supramolecular hierarchical structures and phase behaviors of two giant shape amphiphiles, C60-C8-C12 and BPOSS-LIND, in bulk were studied and both of them were found to form layered structures because of their commensurate building blocks in size. In addition, the first study on the supramolecular structure of a giant polyhedron, C-tetra-BPOSS, was conducted and found it forms a cylinder-like supramolecular structure induced by the molecular architecture and the crystallization of BPOSS cages. Finally, the self-assembled morphologies of 3-component AC60-based and FPOSS-based giant surfactants in thin films were studied, especially the morphological transition with volume fractions change and the topological effect on the morphologies. Because of the affinities of the building blocks, AC60-based giant surfactants are analogues of ABA-type terpolymers and form 2-component morphologies while FPOSS-based ones are analogues of ABC-type terpolymers and form 3-component morphologies. In general, the self-assembled structures of these giant molecules are profoundly affected by the physical interactions among MNPs. The molecular architectures and the selection and proportion of counter parts in a molecule have been proved able to fine tune the supramolecular structures. These understanding of self-assembly of giant molecules allow us to modularly develop novel nanomaterials with desired supramolecular structures consist of specific MNPs of targeting properties.
Stephen Cheng, Dr. (Advisor)
Toshikazu Miyoshi, Dr. (Committee Chair)
Darrell Reneker, Dr. (Committee Member)
Yu Zhu, Dr. (Committee Member)
Xiong Gong, Dr. (Committee Member)
264 p.

Recommended Citations

Citations

  • Hsu, C.-H. (2014). Hierarchical Supramolecular Structures based on Molecular Nanoparticles from Bulk to Thin Film State [Doctoral dissertation, University of Akron]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=akron1406630381

    APA Style (7th edition)

  • Hsu, Chih-Hao. Hierarchical Supramolecular Structures based on Molecular Nanoparticles from Bulk to Thin Film State. 2014. University of Akron, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=akron1406630381.

    MLA Style (8th edition)

  • Hsu, Chih-Hao. "Hierarchical Supramolecular Structures based on Molecular Nanoparticles from Bulk to Thin Film State." Doctoral dissertation, University of Akron, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=akron1406630381

    Chicago Manual of Style (17th edition)