Full metadata record
DC Field | Value | Language |
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dc.contributor.advisor | 남원우 | - |
dc.contributor.author | 김혜연 | - |
dc.creator | 김혜연 | - |
dc.date.accessioned | 2023-02-24T16:30:20Z | - |
dc.date.available | 2023-02-24T16:30:20Z | - |
dc.date.issued | 2023 | - |
dc.identifier.other | OAK-000000201958 | - |
dc.identifier.uri | https://dcollection.ewha.ac.kr/common/orgView/000000201958 | en_US |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/264053 | - |
dc.description.abstract | Metalloenzymes, where iron is the central metal, can activate dioxygen and redox-inactive metal ions such as Ca2+ and Zn2+ are one of the most important co-factors involved in dioxygen activation by metalloenzymes. This thesis reports the study of the generation, characterization and reactivity of a mononuclear nonheme iron(III)-peroxo intermediate bearing 1,4,7,10-tetrabenzyl-1,4,7,10-tetraazacyclotridecane (13-TBC) ligand. This thesis consists of two topics: (1) an electrophilic reactivity of a mononuclear nonheme Fe(III)-peroxo species bearing 13-TBC ligand and (2) a series of (13-TBC)Fe(III)-peroxo complex binding redox-inactive metal ions. The effect of ligands may play the important role on the physicochemical properties of the O2 moiety of iron(III)-peroxo species. Herein, an iron(III)-peroxo complex bearing 13-TBC ([FeⅢ(O2)(13-TBC)]+), which is a ligand in which four methyl groups on the cyclam framework of 13-TMC are replaced with bulkier benzyl groups, was synthesized and characterized by various spectroscopic techniques. Interestingly, [FeIII(O2)(13-TBC)]+ species showed an electrophilic reactivity. For comparison with [FeIII(O2)(13-TBC)]+ in the electrophilic reaction, a series of [FeIII(O2)(13-TBC)]+ binding redox-inactive metal ions ([FeIII(O2)(13-TBC)]+-Mn+) were also synthesized and characterized by various spectroscopic techniques.;금속효소, 그 중에서도 단핵 철-산소 복합체은 다양한 생물학적 반응을 수행하는 핵심 중간 생성물로서 산소를 활성화하며, 산화-환원 비활성 금속 또한 이와 관련된 중요한 보조 인자 중 하나이다. 본 연구에서는 13-TBC 리간드를 가지는 단핵 비헴 철(III)-퍼옥소, [FeIII(O2)(13-TBC)]+ 중간체의 친전자성 반응성 및 레독스 비활성 금속 이온이 결합된 갖는 철(III)-퍼옥소 중간체를 연구하였다. 부피가 큰 치환기를 가진 철(III)-퍼옥소 복합체를 합성하고, 저온 이온화 질량 분석, 전자 상자성 공명 분광법 및 공명 라만 분광법 등 다양한 분광 기술을 사용하여 특성을 명확하게 밝혔다. 이러한 철(III)-퍼옥소 중간체는 다른 금속-퍼옥소 중간체와 달리 친전자성 반응성을 보여주었다. 또한 레독스 비활성 금속 이온이 결합된 비헴성 철(III)-퍼옥소 종인 [FeⅢ(O2)(13-TBC)]+-Mn+을 생성시켜 그 특성을 확인하였다. 결합되는 금속 이온에 따라 최대 흡광 밴드가 달라지며, 이는 루이스 산도와 관련이 있다는 것을 알아냈고 또한 순환 전압 전류법을 통해 전기화학적 특성이 결정되었다. | - |
dc.description.tableofcontents | Chapter I. An Electrophilic Reactivity of a Nonheme Fe(III)-Peroxo Complex Bearing 13-TBC Ligand 7 Abstract 8 I.1. Introduction 9 I.2. Experimental Section 11 I.2.1. Materials 11 I.2.2. Instrumentation 11 I.2.3. Generation of [FeIII(O2)(13-TBC)]+ Species 12 I.2.4. Kinetic Measurements 13 I.3. Results and Discussion 14 I.3.1. Characterization of [FeIII(O2)(13-TBC)]+ 14 I.3.2. Oxygen Atom Transfer Reactions by [FeIII(O2)(13-TBC)]+ 22 I.3.3. Hydrogen Atom Transfer Reactions by [FeIII(O2)(13-TBC)]+ 27 I.4. Conclusion 32 I.5. References 33 Chapter II. A Series of (13-TBC)Fe(III)-Peroxo Complex Binding Redox-Inactive Metal Ions 37 Abstract 38 II.1. Introduction 39 II.2. Experimental Section 40 II.2.1. Materials 40 II.2.2. Instrumentation 40 II.2.3. Generation of [FeⅢ(O2)(13-TBC)]+-Mn+ Species 41 II.3. Results and Discussion 42 II.3.1. Generation of [FeⅢ(O2)(13-TBC)]+-Mn+ 42 II.3.2. Characterization of [FeⅢ(O2)(13-TBC)]+-Mn+ 47 II.3.3. Electrochemical properties of [FeⅢ(O2)(13-TBC)]+-Mn+ 50 II.4. Conclusion 52 II.5. References 53 | - |
dc.format | application/pdf | - |
dc.format.extent | 1250898 bytes | - |
dc.language | eng | - |
dc.publisher | 이화여자대학교 대학원 | - |
dc.subject.ddc | 500 | - |
dc.title | Synthesis, Characterization and Reactivity of a Mononuclear Nonheme Iron(III)-Peroxo Complex Bearing 13-TBC Ligand | - |
dc.type | Master's Thesis | - |
dc.creator.othername | Kim, Hyeyeon | - |
dc.format.page | xi, 62 p. | - |
dc.identifier.thesisdegree | Master | - |
dc.identifier.major | 대학원 화학·나노과학과 | - |
dc.date.awarded | 2023. 2 | - |