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Metal and mineral catalyzed organic photochemistry in modern and prebiotic environments- [electronic resource]
Metal and mineral catalyzed organic photochemistry in modern and prebiotic environments- [electronic resource]
상세정보
- 자료유형
- 학위논문(국외)
- 자관 청구기호
- 기본표목-개인명
- 표제와 책임표시사항
- Metal and mineral catalyzed organic photochemistry in modern and prebiotic environments - [electronic resource] / Mangiante, David Michael.
- 발행, 배포, 간사 사항
- 형태사항
- 1 online resource(67 p)
- 일반주기
- Source: Dissertation Abstracts International, Volume: 78-06(E), Section: B.
- 일반주기
- Adviser: Jillian Banfield.
- 학위논문주기
- Thesis (Ph.D.)--University of California, Berkeley, 2016.
- 요약 등 주기
- 요약Minerals and metals serve important roles in the organic geochemistry of natural environments. Mobility of organics, catalysis of degradation, and redox catalysis are among the processes affected by minerals. With the addition of ultraviolet light a new suite of photo-induced redox reactions is possible including reductive and oxidative ligand-to-metal/mineral charge transfer. Such reactions allow for novel chemistry that has relevance to the modern Earth as well as the pre-biotic origin of life.
- 요약 등 주기
- 요약This thesis describes processes by which electrons transfer between minerals/metals and organic ligands relevant to natural systems as well as the origins of life. I present evidence of ultrafast electron transfer and the production of radical intermediates essential to deducing redox reaction mechanisms. I also present methods for communicating understanding of interfacial chemistry to the public that promote engagement in science. This thesis is broadly applicable to those interested in mineral organic photochemistry, electron transfer, the origin of life, and science teaching methods.
- 요약 등 주기
- 요약I probed the chemistry between organic molecules and minerals/metals, using pump/probe transient absorption (TA) spectroscopy to observe the dynamics of electrons and vibrational modes at timescales ranging from picoseconds to nanoseconds. This technique can be conducted in solution and can be highly sensitive to intermediate reaction products.
- 요약 등 주기
- 요약I examined the photolysis of the metal carboloto, ferric oxalate, under UV irradiation using mid-infrared TA spectroscopy in both D2O and H2O. Ferric oxalate is a model molecule for natural systems and is used to measure photo flux due to its well-characterized quantum efficiency. However, the mechanism of its photolysis is debated. This was the first time the intermediates of ferric oxalate photolysis were observed using techniques sensitive to the vibrational states of organic molecules. I observed the rapid intramolecular charge transfer and the production of CO2 and tentatively CO2•--. Additionally, we observed intermediate states that we interpret to be CO2 disassociating from ferrous iron, a signature never before reported.
- 요약 등 주기
- 요약Investigations of photo-induced electron transfer were expanded to ZnS nanoparticles and fumarate. Fumarate is an intermediate metabolite in the tricarboxilic acid (TCA) cycle, which is a part of core metabolism in modern organisms. It undergoes a two-electron reduction to form succinate. Reductive versions of the TCA cycle may have been important for the origin of prebiotic metabolism. I measured the effect of adsorbed fumarate on the electronic states of photo-excited ZnS and observed electron transfer both at short (1 ns) timescales. Additionally, I observed an electronic signature tentatively attributed to fumarate radical, which persisted for at least 8 nanoseconds. The appearance of a long-lived radical intermediate product and the rapid initial electron transfer from the mineral to the organic suggests that ZnS could be a viable catalyst for prebiotic metabolism on the early Earth.
- 요약 등 주기
- 요약To better educate students on the importance of mineral surface chemistry I designed and implemented a classroom experiment wherein students performed electrolysis of water using mineral electrodes. The experiment emphasized both the mineral catalysis and mineral redox chemistry, which occur at the solid/liquid interface. Concepts in interfacial chemistry are often difficult to exhibit, making this teaching tool unique and useful. Students were guided through a set of investigations and constructed their understanding through observations and sharing of ideas. The experiment was successfully implemented in a college level mineralogy course.
- 주제명부출표목-일반주제명
- 부출표목-단체명
- 기본자료저록
- Dissertation Abstracts International. 78-06B(E).
- 기본자료저록
- Dissertation Abstract International
- 전자적 위치 및 접속
- 원문정보보기
- 소장사항
-
20170404 2017
MARC
008170601s2016 us esm 001c eng■001MOKWON01254160
■00520170418120202
■007cr
■020 ▼a9781369559439
■035 ▼a(MiAaPQ)AAI10192805
■040 ▼aMiAaPQ▼cMiAaPQ
■090 ▼a전자도서(박사논문)
■1001 ▼aMangiante, David Michael.
■24510▼aMetal and mineral catalyzed organic photochemistry in modern and prebiotic environments▼h[electronic resource]▼cMangiante, David Michael.
■260 ▼a[Sl]▼bUniversity of California, Berkeley▼c2016
■300 ▼a1 online resource(67 p)
■500 ▼aSource: Dissertation Abstracts International, Volume: 78-06(E), Section: B.
■500 ▼aAdviser: Jillian Banfield.
■5021 ▼aThesis (Ph.D.)--University of California, Berkeley, 2016.
■520 ▼aMinerals and metals serve important roles in the organic geochemistry of natural environments. Mobility of organics, catalysis of degradation, and redox catalysis are among the processes affected by minerals. With the addition of ultraviolet light a new suite of photo-induced redox reactions is possible including reductive and oxidative ligand-to-metal/mineral charge transfer. Such reactions allow for novel chemistry that has relevance to the modern Earth as well as the pre-biotic origin of life.
■520 ▼aThis thesis describes processes by which electrons transfer between minerals/metals and organic ligands relevant to natural systems as well as the origins of life. I present evidence of ultrafast electron transfer and the production of radical intermediates essential to deducing redox reaction mechanisms. I also present methods for communicating understanding of interfacial chemistry to the public that promote engagement in science. This thesis is broadly applicable to those interested in mineral organic photochemistry, electron transfer, the origin of life, and science teaching methods.
■520 ▼aI probed the chemistry between organic molecules and minerals/metals, using pump/probe transient absorption (TA) spectroscopy to observe the dynamics of electrons and vibrational modes at timescales ranging from picoseconds to nanoseconds. This technique can be conducted in solution and can be highly sensitive to intermediate reaction products.
■520 ▼aI examined the photolysis of the metal carboloto, ferric oxalate, under UV irradiation using mid-infrared TA spectroscopy in both D2O and H2O. Ferric oxalate is a model molecule for natural systems and is used to measure photo flux due to its well-characterized quantum efficiency. However, the mechanism of its photolysis is debated. This was the first time the intermediates of ferric oxalate photolysis were observed using techniques sensitive to the vibrational states of organic molecules. I observed the rapid intramolecular charge transfer and the production of CO2 and tentatively CO2•--. Additionally, we observed intermediate states that we interpret to be CO2 disassociating from ferrous iron, a signature never before reported.
■520 ▼aInvestigations of photo-induced electron transfer were expanded to ZnS nanoparticles and fumarate. Fumarate is an intermediate metabolite in the tricarboxilic acid (TCA) cycle, which is a part of core metabolism in modern organisms. It undergoes a two-electron reduction to form succinate. Reductive versions of the TCA cycle may have been important for the origin of prebiotic metabolism. I measured the effect of adsorbed fumarate on the electronic states of photo-excited ZnS and observed electron transfer both at short (1 ns) timescales. Additionally, I observed an electronic signature tentatively attributed to fumarate radical, which persisted for at least 8 nanoseconds. The appearance of a long-lived radical intermediate product and the rapid initial electron transfer from the mineral to the organic suggests that ZnS could be a viable catalyst for prebiotic metabolism on the early Earth.
■520 ▼aTo better educate students on the importance of mineral surface chemistry I designed and implemented a classroom experiment wherein students performed electrolysis of water using mineral electrodes. The experiment emphasized both the mineral catalysis and mineral redox chemistry, which occur at the solid/liquid interface. Concepts in interfacial chemistry are often difficult to exhibit, making this teaching tool unique and useful. Students were guided through a set of investigations and constructed their understanding through observations and sharing of ideas. The experiment was successfully implemented in a college level mineralogy course.
■590 ▼aSchool code: 0028.
■650 4▼aGeochemistry
■690 ▼a0996
■71020▼aUniversity of California, Berkeley▼bEarth and Planetary Science.
■7730 ▼tDissertation Abstracts International▼g78-06B(E).
■773 ▼tDissertation Abstract International
■790 ▼a0028
■791 ▼aPh.D.
■792 ▼a2016
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T14489911▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
■980 ▼a20170404▼f2017
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