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Giant Molecules Based on Functionalized Fullerenes: Precise Synthesis and Diverse Assembly Behaviors

Lin, Zhiwei
http://rave.ohiolink.edu/etdc/view?acc_num=akron1468848837

Abstract Details

2016, Doctor of Philosophy, University of Akron, Polymer Science.
The emergence of giant molecules built up from molecular nanoparticles (MNP) based nanoatoms has attracted substantial attentions because of their unique molecular design with shape and interaction anisotropy as well as conformation rigidity, leading to intriguing self-assembly behaviors different from traditional building blocks. Numerous hierarchically assembled structures deriving from giant molecules have been theoretically predicted by computer simulation. However, experimental exploration is still in the infancy. In this dissertation, we are aiming to develop several categories of giant molecules based on precisely functionalized fullerene (C60), and study their versatile self-assembly behaviors. To break symmetry, hydrophilic C60-based nanoatoms are designed, bearing multiple carboxyl acid (AC60) or hydroxyl groups (DC60). They are hexa-adducts of C60 with precisely defined chemical structures, synthesized by Bingel reaction. Various giant molecules can be achieved through attaching different hydrophobic building blocks onto these hydrophilic C60 via “click” chemistry. First of all, two molecular Janus particles with different molecular architectures were obtained by tethering an AC60 with one (AC60-C60) or two (AC60-2C60) hydrophobic C60. Investigation on the solution self-assembly behavior of these two molecular Janus particles reveals that molecular architectures and solvent polarity are critical parameters in determining the assembled structures. Moreover, the conjugation of AC60 with a cyclic polystyrene (CPS) using sequential click approaches gave rise to a set of novel giant molecules, which are referred to as “nano-diamond-ring-like” giant surfactants. They possess particular molecular structures, and may exhibit completely different self-assembly behaviors from the traditional self-assembly building blocks. We then extend such studies on the assembly of giant molecules in condensed state by synthesizing giant molecules composed of one AC60 tethered by PS-b-polyethylene oxide (PEO), as well as one DC60 tethered by one to four PS chains. Specifically, several pairs of topological isomers are designed, possessing identical overall molecule masses but with different topologies. Driven by the strong segregation between the hydrophilic C60 and hydrophobic PS, a variety of well-ordered structures with feature size below 10 nm are created. It was also demonstrated that the formation of assembled structures is extremely sensitive to their molecular topologies. The formation mechanism of these well-ordered nanostructures is fully discussed.
Stephen Cheng (Advisor)
Toshikazu Miyoshi (Committee Chair)
Tianbo Liu (Committee Member)
Abraham Joy (Committee Member)
Chrys Wesdemiotis (Committee Member)
205 p.
Chemistry; Materials Science; Polymer Chemistry; Polymers
Fullerenes, Self-assembly, Giant molecules, Precise synthesis, Small angle X-ray scattering , Transmission electron microscopy

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Citations

  • Lin, Z. (2016). Giant Molecules Based on Functionalized Fullerenes: Precise Synthesis and Diverse Assembly Behaviors [Doctoral dissertation, University of Akron]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=akron1468848837

    APA Style (7th edition)

  • Lin, Zhiwei. Giant Molecules Based on Functionalized Fullerenes: Precise Synthesis and Diverse Assembly Behaviors. 2016. University of Akron, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=akron1468848837.

    MLA Style (8th edition)

  • Lin, Zhiwei. "Giant Molecules Based on Functionalized Fullerenes: Precise Synthesis and Diverse Assembly Behaviors." Doctoral dissertation, University of Akron, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=akron1468848837

    Chicago Manual of Style (17th edition)

akron1468848837
177
© 2016, all rights reserved.
This open access ETD is published by University of Akron and OhioLINK.