Design and synthesis of diarylethene photoswitches: from photochemical properties to switchable fluorescence and photopharmacology
<p>This thesis presents an investigation into diarylethene-based organic photoswitches, with emphasis on optimizing their photoswitching capabilities. The research then progresses to implement these enhanced photoswitches in practical applications, specifically focusing on switchable fluoresce...
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| Format: | Thesis |
| Language: | English |
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2024
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| _version_ | 1826314665715564544 |
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| author | Qiu, S |
| author2 | Cadoni, E |
| author_facet | Cadoni, E Qiu, S |
| author_sort | Qiu, S |
| collection | OXFORD |
| description | <p>This thesis presents an investigation into diarylethene-based organic photoswitches, with emphasis on optimizing their photoswitching capabilities. The research then progresses to implement these enhanced photoswitches in practical applications, specifically focusing on switchable fluorescence systems and photopharmacology.</p>
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<p><strong>Chapter 1</strong> provides a review of molecular photoswitch research, elucidating fundamental models, quantitative formalisms, and key photoswitching performance parameters. A comparative analysis of various photoswitch classes is presented, highlighting their structural and photochemical features. This analysis identifies diarylethenes as a promising class of photoswitch for further optimization.</p>
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<p><strong>Chapter 2</strong> describes the synthesis and characterization of push-push, pull-pull, and push-pull diarylethenes with varying lengths of conjugation. A comprehensive examination of their photophysical and photochemical properties is presented, with observed trends rationalized through DFT and TD-DFT calculations, and conformational sampling. The chapter culminates in the identification of a water-soluble diarylethene, featuring two N-methylpyridinium groups with alkyne spacers, capable of bidirectional visible light photoswitching with quantitative photostationary state distribution.</p>
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<p><strong>Chapter 3</strong> extends the findings of Chapter 2, utilizing the optimized diarylethene to develop two photoswitchable fluorophores based on a diarylethene-cyanine dyad design. The diarylethene functions as a photocontrollable switch for the fluorophore, enabling reversible transitions between fluorescent and non-fluorescent states. The chapter details the synthesis of these photoswitchable dyads and provides an in-depth characterization of their fluorescence switching properties and fatigue resistance.</p>
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<p><strong>Chapter 4</strong> explores diarylethenes as photoswitchable ligands targeting G-quadruplexes. The synthesis of four diarylethene-based switchable ligands is outlined, followed by an examination of their binding interactions with G-quadruplexes. This chapter reveals that the open and closed isomers of the diarylethenes exhibit distinct affinities for G-quadruplexes and varying degrees of cytotoxicity.</p>
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<p><strong>Chapter 5</strong> summarizes the key findings of the research and provides a critical outlook for future investigations in this field.</p> |
| first_indexed | 2024-12-09T03:08:46Z |
| format | Thesis |
| id | oxford-uuid:0164082c-ce49-41e4-bee9-f423be607477 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-12-09T03:08:46Z |
| publishDate | 2024 |
| record_format | dspace |
| spelling | oxford-uuid:0164082c-ce49-41e4-bee9-f423be6074772024-10-07T10:28:17ZDesign and synthesis of diarylethene photoswitches: from photochemical properties to switchable fluorescence and photopharmacologyThesishttp://purl.org/coar/resource_type/c_db06uuid:0164082c-ce49-41e4-bee9-f423be607477Organic chemistryChemistryPhotochemistryEnglishHyrax Deposit2024Qiu, SCadoni, EAnderson, HLMonti, L<p>This thesis presents an investigation into diarylethene-based organic photoswitches, with emphasis on optimizing their photoswitching capabilities. The research then progresses to implement these enhanced photoswitches in practical applications, specifically focusing on switchable fluorescence systems and photopharmacology.</p> <br> <p><strong>Chapter 1</strong> provides a review of molecular photoswitch research, elucidating fundamental models, quantitative formalisms, and key photoswitching performance parameters. A comparative analysis of various photoswitch classes is presented, highlighting their structural and photochemical features. This analysis identifies diarylethenes as a promising class of photoswitch for further optimization.</p> <br> <p><strong>Chapter 2</strong> describes the synthesis and characterization of push-push, pull-pull, and push-pull diarylethenes with varying lengths of conjugation. A comprehensive examination of their photophysical and photochemical properties is presented, with observed trends rationalized through DFT and TD-DFT calculations, and conformational sampling. The chapter culminates in the identification of a water-soluble diarylethene, featuring two N-methylpyridinium groups with alkyne spacers, capable of bidirectional visible light photoswitching with quantitative photostationary state distribution.</p> <br> <p><strong>Chapter 3</strong> extends the findings of Chapter 2, utilizing the optimized diarylethene to develop two photoswitchable fluorophores based on a diarylethene-cyanine dyad design. The diarylethene functions as a photocontrollable switch for the fluorophore, enabling reversible transitions between fluorescent and non-fluorescent states. The chapter details the synthesis of these photoswitchable dyads and provides an in-depth characterization of their fluorescence switching properties and fatigue resistance.</p> <br> <p><strong>Chapter 4</strong> explores diarylethenes as photoswitchable ligands targeting G-quadruplexes. The synthesis of four diarylethene-based switchable ligands is outlined, followed by an examination of their binding interactions with G-quadruplexes. This chapter reveals that the open and closed isomers of the diarylethenes exhibit distinct affinities for G-quadruplexes and varying degrees of cytotoxicity.</p> <br> <p><strong>Chapter 5</strong> summarizes the key findings of the research and provides a critical outlook for future investigations in this field.</p> |
| spellingShingle | Organic chemistry Chemistry Photochemistry Qiu, S Design and synthesis of diarylethene photoswitches: from photochemical properties to switchable fluorescence and photopharmacology |
| title | Design and synthesis of diarylethene photoswitches: from photochemical properties to switchable fluorescence and photopharmacology |
| title_full | Design and synthesis of diarylethene photoswitches: from photochemical properties to switchable fluorescence and photopharmacology |
| title_fullStr | Design and synthesis of diarylethene photoswitches: from photochemical properties to switchable fluorescence and photopharmacology |
| title_full_unstemmed | Design and synthesis of diarylethene photoswitches: from photochemical properties to switchable fluorescence and photopharmacology |
| title_short | Design and synthesis of diarylethene photoswitches: from photochemical properties to switchable fluorescence and photopharmacology |
| title_sort | design and synthesis of diarylethene photoswitches from photochemical properties to switchable fluorescence and photopharmacology |
| topic | Organic chemistry Chemistry Photochemistry |
| work_keys_str_mv | AT qius designandsynthesisofdiarylethenephotoswitchesfromphotochemicalpropertiestoswitchablefluorescenceandphotopharmacology |