Design and synthesis of polymechanophore systems with dramatic mechanochemical response
Abstract/Contents
- Abstract
- Polymer mechanochemistry is an emerging area of research that investigates the use of mechanical force to promote chemical transformations. Embedding properly designed mechanochemically active motifs, termed mechanophores into polymers can induce various force triggered responses including coloration, chemiluminescence, small molecule release, and catalysis. However, most examples in this field only incorporate a tiny amount of mechanophores into a mechanochemically inert polymer. The low content of mechanophore loadings limits the magnitude of mechanical response of the materials. In this thesis, we introduce a family of mechanophore monomers based on fused bicyclohexene structure, which can be efficiently polymerized through ring-opening metathesis polymerization (ROMP) into well-controlled polymechanophores with unprecedented mechanophore loading. The modular mechanophore design can be divided into three parts: a readily polymerizable cyclobutene head, a mechanochemically active cyclobutane core and a fused cycle with different functionalities. Upon force activation, cyclobutane can readily isomerize into a pair of alkenes, while revealing the "hidden" functionalities attached and incorporating them into polymer main chain. Through the choice of different functionalized cycles, we can achieve dramatic changes in polymer properties including conjugation state, degradability, contour length and binding affinity towards certain guest molecules. In Chapter 1, we will introduce the history, recent developments, and current challenges in this field. Chapter 2 and 3 summarize our efforts to develop mechanochemically generated conjugated polymers with better scalability and structural tunability. Chapter 4 introduces a polymer system with force-enhanced degradability by mechanochemically transforming hydrolytically stable cyclic ether into acid labile enol ether. Chapter 5 describes the development of a rotaxane based mechanophore that exhibits controlled force-triggered release behavior. Chapter 6 describes a side project I worked on about the controlled synthesis of metathesis degradable polycyclohexenes through the alternating copolymerization between butadiene and methyl methacrylate.
Description
| Type of resource | text |
|---|---|
| Form | electronic resource; remote; computer; online resource |
| Extent | 1 online resource. |
| Place | California |
| Place | [Stanford, California] |
| Publisher | [Stanford University] |
| Copyright date | 2022; ©2022 |
| Publication date | 2022; 2022 |
| Issuance | monographic |
| Language | English |
Creators/Contributors
| Author | Yang, Jinghui |
|---|---|
| Degree supervisor | Xia, Yan, 1980- |
| Thesis advisor | Xia, Yan, 1980- |
| Thesis advisor | Burns, Noah |
| Thesis advisor | Martinez, Todd J. (Todd Joseph), 1968- |
| Degree committee member | Burns, Noah |
| Degree committee member | Martinez, Todd J. (Todd Joseph), 1968- |
| Associated with | Stanford University, Department of Chemistry |
Subjects
| Genre | Theses |
|---|---|
| Genre | Text |
Bibliographic information
| Statement of responsibility | Jinghui Yang. |
|---|---|
| Note | Submitted to the Department of Chemistry. |
| Thesis | Thesis Ph.D. Stanford University 2022. |
| Location | https://purl.stanford.edu/dy191yf2755 |
Access conditions
- Copyright
- © 2022 by Jinghui Yang
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