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Enabling In Vivo Catalytic Activation of Bioorthogonal Chemistry with Light Using Si-Rhodamine and the Universal and Modular Synthesis of Monoaryltetrazines from Functionalized Arylboronic Acids.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Enabling In Vivo Catalytic Activation of Bioorthogonal Chemistry with Light Using Si-Rhodamine and the Universal and Modular Synthesis of Monoaryltetrazines from Functionalized Arylboronic Acids./
作者:	Wang, Chuanqi.
面頁冊數:	1 online resource (289 pages)
附註:	Source: Dissertations Abstracts International, Volume: 84-04, Section: B.
Contained By:	Dissertations Abstracts International84-04B.
標題:	Chemistry. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=29328191click for full text (PQDT)
ISBN:	9798351458007

Enabling In Vivo Catalytic Activation of Bioorthogonal Chemistry with Light Using Si-Rhodamine and the Universal and Modular Synthesis of Monoaryltetrazines from Functionalized Arylboronic Acids.
Wang, Chuanqi.

Enabling In Vivo Catalytic Activation of Bioorthogonal Chemistry with Light Using Si-Rhodamine and the Universal and Modular Synthesis of Monoaryltetrazines from Functionalized Arylboronic Acids. - 1 online resource (289 pages)

Source: Dissertations Abstracts International, Volume: 84-04, Section: B.

Thesis (Ph.D.)--University of Delaware, 2022.

Includes bibliographical references

Tetrazine (Tz) ligation is a useful tool to probe the biochemistry in living organisms, due to its rapid catalyst-free kinetics, innocuous byproducts, and orthogonality toward native cellular processes. In the first chapter, I will give a brief introduction to the development of tetrazine ligation as a bioorthogonal chemical reaction, and the application of tetrazine ligation to different fields like cell imaging, and medicinal chemistry, protein synthesis, and materials science. My graduate research had been focusing on developing new catalysts and reagents to empower this chemical tool. In chapter 2, I will talk about the first cytocompatible photocatalyst that will activate tetrazine ligation in vivo, which was repurposed from a widely used chromophore. Chromophores that absorb in the tissue-penetrant far-red/near-infrared window have long served as photocatalysts to generate singlet oxygen for photodynamic therapy. However, the cytotoxicity and side reactions associated with singlet oxygen sensitization have posed a problem for using long-wavelength photocatalysis to initiate other types of chemical reactions in biological environments. Herein, silicon-Rhodamine compounds (SiRs) are described as photocatalysts for inducing rapid bioorthogonal chemistry using 660 nm light through the oxidation of a dihydrotetrazine to a tetrazine in the presence of trans-cyclooctene dienophiles. SiRs have been commonly used as fluorophores for bioimaging but have not been applied to catalyze chemical reactions. A series of SiR derivatives were evaluated, and the Janelia Fluor-SiR dyes were found to be especially effective in catalyzing photooxidation (typically 3%). A dihydrotetrazine (DHT)/tetrazine pair is described that displays high stability in both oxidation states. A protein that was site-selectively modified by trans-cyclooctene (TCO) was quantitatively conjugated upon exposure to 660 nm light and a dihydrotetrazine. By contrast, a previously described methylene blue catalyst was found to rapidly degrade the protein. SiR-red light photocatalysis was used to cross-link hyaluronic acid (HA) derivatives functionalized by dihydrotetrazine and trans-cyclooctenes, enabling 3D culture of human prostate cancer cells. Photoinducible hydrogel formation could also be carried out in live mice through subcutaneous injection of a Cy7-labeled hydrogel precursor solution, followed by brief irradiation to produce a stable hydrogel. This cytocompatible method for using red light photocatalysis to activate bioorthogonal chemistry is anticipated to find broad applications where spatiotemporal control is needed in biological environments.In chapter 3, while reviewing known methodology to synthesize and modify tetrazines, I will also describe the development of a new reagent 'h-Tz', which could be safely prepared and could be used for the universal and modular synthesis of mono-aryltetrazines from functionalized arylboronic acids using and Ag-mediated Liebeskind-Srogl cross-coupling.

Electronic reproduction.
Ann Arbor, Mich. :
ProQuest,
2023

Mode of access: World Wide Web

ISBN: 9798351458007Subjects--Topical Terms:

516420
Chemistry.
Subjects--Index Terms:

Catalytic activationIndex Terms--Genre/Form:

542853
Electronic books.

Enabling In Vivo Catalytic Activation of Bioorthogonal Chemistry with Light Using Si-Rhodamine and the Universal and Modular Synthesis of Monoaryltetrazines from Functionalized Arylboronic Acids.
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520 $a Tetrazine (Tz) ligation is a useful tool to probe the biochemistry in living organisms, due to its rapid catalyst-free kinetics, innocuous byproducts, and orthogonality toward native cellular processes. In the first chapter, I will give a brief introduction to the development of tetrazine ligation as a bioorthogonal chemical reaction, and the application of tetrazine ligation to different fields like cell imaging, and medicinal chemistry, protein synthesis, and materials science. My graduate research had been focusing on developing new catalysts and reagents to empower this chemical tool. In chapter 2, I will talk about the first cytocompatible photocatalyst that will activate tetrazine ligation in vivo, which was repurposed from a widely used chromophore. Chromophores that absorb in the tissue-penetrant far-red/near-infrared window have long served as photocatalysts to generate singlet oxygen for photodynamic therapy. However, the cytotoxicity and side reactions associated with singlet oxygen sensitization have posed a problem for using long-wavelength photocatalysis to initiate other types of chemical reactions in biological environments. Herein, silicon-Rhodamine compounds (SiRs) are described as photocatalysts for inducing rapid bioorthogonal chemistry using 660 nm light through the oxidation of a dihydrotetrazine to a tetrazine in the presence of trans-cyclooctene dienophiles. SiRs have been commonly used as fluorophores for bioimaging but have not been applied to catalyze chemical reactions. A series of SiR derivatives were evaluated, and the Janelia Fluor-SiR dyes were found to be especially effective in catalyzing photooxidation (typically 3%). A dihydrotetrazine (DHT)/tetrazine pair is described that displays high stability in both oxidation states. A protein that was site-selectively modified by trans-cyclooctene (TCO) was quantitatively conjugated upon exposure to 660 nm light and a dihydrotetrazine. By contrast, a previously described methylene blue catalyst was found to rapidly degrade the protein. SiR-red light photocatalysis was used to cross-link hyaluronic acid (HA) derivatives functionalized by dihydrotetrazine and trans-cyclooctenes, enabling 3D culture of human prostate cancer cells. Photoinducible hydrogel formation could also be carried out in live mice through subcutaneous injection of a Cy7-labeled hydrogel precursor solution, followed by brief irradiation to produce a stable hydrogel. This cytocompatible method for using red light photocatalysis to activate bioorthogonal chemistry is anticipated to find broad applications where spatiotemporal control is needed in biological environments.In chapter 3, while reviewing known methodology to synthesize and modify tetrazines, I will also describe the development of a new reagent 'h-Tz', which could be safely prepared and could be used for the universal and modular synthesis of mono-aryltetrazines from functionalized arylboronic acids using and Ag-mediated Liebeskind-Srogl cross-coupling.
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538 $a Mode of access: World Wide Web
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653 $a Arylboronic acid
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