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Photoinduced Electron Transfer for Protecting Groups and Polymer Synthesis
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| 자료유형 | 학위논문 |
|---|---|
| 서명/저자사항 | Photoinduced Electron Transfer for Protecting Groups and Polymer Synthesis. |
| 개인저자 | Thum, Matthew David. |
| 단체저자명 | University of Maryland, College Park. Chemistry. |
| 발행사항 | [S.l.]: University of Maryland, College Park., 2019. |
| 발행사항 | Ann Arbor: ProQuest Dissertations & Theses, 2019. |
| 형태사항 | 245 p. |
| 기본자료 저록 | Dissertations Abstracts International 81-05B. Dissertation Abstract International |
| ISBN | 9781687924216 |
| 학위논문주기 | Thesis (Ph.D.)--University of Maryland, College Park, 2019. |
| 일반주기 |
Source: Dissertations Abstracts International, Volume: 81-05, Section: B.
Advisor: Falvey, Daniel E. |
| 이용제한사항 | This item must not be sold to any third party vendors. |
| 요약 | Using light to drive chemical reactions affords spatial and temporal control not typically displayed in thermal chemistry. For this reason, light induced transformations have been used in the manufacturing of polymers and plastics, and in the development of systems that require precise activation, such as drug delivery. The work presented in this dissertation will involve photoinduced electron transfer (PET) and its applications in protecting groups and polymer synthesis.Chapter 1 will discuss photoinduced electron transfer and its theory. Examples will be provided to demonstrate how it has been used as a trigger in photoremovable protecting groups, and as the mechanism of initiation in controlled radical polymerization. In Chapter 2, three different protecting groups triggered by PET will be analyzed. The analysis of key intermediates involved in the mechanism will be performed using nanosecond transient absorption spectroscopy. Chapter 3 willdiscuss the adaptation of an N-alkyl picoloinum protecting group to be activated by stepwise absorption of two photons of visible light.Chapter 4 will explore the photophysical properties of commonly used chain transfer agents for controlled radical polymerization. The behavior of the chain transfer agents under ultra violet and visible light photolysis, electron transfer, and energy transfer will be examined. Chapter 5 will discuss the role of the oxidation of dimethyl sulfoxide (DMSO) in the initiation of polymerization using photoredox catalysts. Our work demonstrates that, under highly oxidative conditions, an electron can be abstracted from DMSO and the resulting DMSO cation radical can degrade to for radicals capable of initiating polymerization. We explore this process for an anthraquinone-base photoredox catalyst, and apply it, along with a chain transfer agent, to the manufacturing of polymers with precise molecular weights and narrow molecular weight distributions. |
| 일반주제명 | Chemistry. Polymer chemistry. Physical chemistry. Organic chemistry. |
| 언어 | 영어 |
| 바로가기 | 
: 이 자료의 원문은 한국교육학술정보원에서 제공합니다. |
