{"id":{"repo_id":"nus","oai_identifier":"oai:scholarbank.nus.edu.sg:10635/319598"},"canonical_url":"https://search.dev.ndltd.org/etd/nus/oai:scholarbank.nus.edu.sg:10635/319598","repository":{"repo_id":"nus","name":"National University of Singapore","base_url":"https://scholarbank.nus.edu.sg/oai/request"},"display":{"title":"ENZYME-LIKE DNA CATALYST DESIGN","abstract":"This work develops DNA as a programmable chiral platform for asymmetric catalysis in water. It first reviews the promise and limitations of DNA-based catalysis: although DNA offers chirality, structural programmability, aqueous compatibility, and sustainability, existing systems are often limited by difficult catalyst construction, narrow Lewis-acid-centered reaction scope, and unclear stereocontrol mechanisms. To address these issues, a chemoenzymatic modification strategy is introduced, combining DNA base excision repair with oxime/hydrazone ligation to install diverse small-molecule catalysts at site-specific AP sites without phosphoramidite synthesis. This modular platform enables rapid preparation of DNA catalysts and delivers highly enantioselective Friedel–Crafts and atroposelective reactions with low catalyst loading and high turnover. The work further demonstrates that DNA phosphate groups can actively control stereoselective ion-pairing catalysis by organizing cationic intermediates near catalytic sites. Phosphorothioate substitution experiments reveal that specific local phosphates govern stereocontrol, while distal phosphates mainly serve as a dynamic ionic reservoir.","abstract_html":"This work develops DNA as a programmable chiral platform for asymmetric catalysis in water. It first reviews the promise and limitations of DNA-based catalysis: although DNA offers chirality, structural programmability, aqueous compatibility, and sustainability, existing systems are often limited by difficult catalyst construction, narrow Lewis-acid-centered reaction scope, and unclear stereocontrol mechanisms. To address these issues, a chemoenzymatic modification strategy is introduced, combining DNA base excision repair with oxime/hydrazone ligation to install diverse small-molecule catalysts at site-specific AP sites without phosphoramidite synthesis. This modular platform enables rapid preparation of DNA catalysts and delivers highly enantioselective Friedel–Crafts and atroposelective reactions with low catalyst loading and high turnover. The work further demonstrates that DNA phosphate groups can actively control stereoselective ion-pairing catalysis by organizing cationic intermediates near catalytic sites. Phosphorothioate substitution experiments reveal that specific local phosphates govern stereocontrol, while distal phosphates mainly serve as a dynamic ionic reservoir.","abstract_has_math":false,"creators":["LI ZHAOYANG"],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2026,"date_issued":"2026-01-12","date_published":"2026-01-12","updated_at":"2026-07-24T03:31:13Z","subjects":["Organic reaction","Ion pairing","DNA repair","Asymmetric catalysis","DNA hybrid catalyst","DNA catalysis"],"languages":[],"rights":[],"rights_urls":["https://scholarbank.nus.edu.sg/bitstreams/ebe61551-59d6-4dfd-bdfd-5fa129f7a2fd/download"],"identifier_entries":[]},"links":{"outbound_url":null,"outbound_label":null,"outbound_source":null},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["LI ZHAOYANG"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.issued","label":"Date","values":["2026-01-12"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["https://scholarbank.nus.edu.sg/handle/10635/319598"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Organic reaction","Ion pairing","DNA repair","Asymmetric catalysis","DNA hybrid catalyst","DNA catalysis"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:rights","label":"Dc Rights","values":["https://scholarbank.nus.edu.sg/bitstreams/ebe61551-59d6-4dfd-bdfd-5fa129f7a2fd/download"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://scholarbank.nus.edu.sg/bitstreams/87fd29bb-66a0-4b23-8d56-4ded5afd6601/download"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["This work develops DNA as a programmable chiral platform for asymmetric catalysis in water. It first reviews the promise and limitations of DNA-based catalysis: although DNA offers chirality, structural programmability, aqueous compatibility, and sustainability, existing systems are often limited by difficult catalyst construction, narrow Lewis-acid-centered reaction scope, and unclear stereocontrol mechanisms. To address these issues, a chemoenzymatic modification strategy is introduced, combining DNA base excision repair with oxime/hydrazone ligation to install diverse small-molecule catalysts at site-specific AP sites without phosphoramidite synthesis. This modular platform enables rapid preparation of DNA catalysts and delivers highly enantioselective Friedel–Crafts and atroposelective reactions with low catalyst loading and high turnover. The work further demonstrates that DNA phosphate groups can actively control stereoselective ion-pairing catalysis by organizing cationic intermediates near catalytic sites. Phosphorothioate substitution experiments reveal that specific local phosphates govern stereocontrol, while distal phosphates mainly serve as a dynamic ionic reservoir."]},{"key":"dc:format.checksum.md5","label":"Dc Format Checksum Md5","values":["9f3c6f2aa8f96291ef77b0a18484521d","2bc48d061298cca344c65fadda2fc4ca","f86031525725116f358b2e41325cd99a"]},{"key":"dc:title","label":"Title","values":["ENZYME-LIKE DNA CATALYST DESIGN"]}]}],"canonical_facts":{"dc:creator":["LI ZHAOYANG"],"dc:date.issued":["2026-01-12"],"dc:description.abstract":["This work develops DNA as a programmable chiral platform for asymmetric catalysis in water. It first reviews the promise and limitations of DNA-based catalysis: although DNA offers chirality, structural programmability, aqueous compatibility, and sustainability, existing systems are often limited by difficult catalyst construction, narrow Lewis-acid-centered reaction scope, and unclear stereocontrol mechanisms. To address these issues, a chemoenzymatic modification strategy is introduced, combining DNA base excision repair with oxime/hydrazone ligation to install diverse small-molecule catalysts at site-specific AP sites without phosphoramidite synthesis. This modular platform enables rapid preparation of DNA catalysts and delivers highly enantioselective Friedel–Crafts and atroposelective reactions with low catalyst loading and high turnover. The work further demonstrates that DNA phosphate groups can actively control stereoselective ion-pairing catalysis by organizing cationic intermediates near catalytic sites. Phosphorothioate substitution experiments reveal that specific local phosphates govern stereocontrol, while distal phosphates mainly serve as a dynamic ionic reservoir."],"dc:format.checksum.md5":["9f3c6f2aa8f96291ef77b0a18484521d","2bc48d061298cca344c65fadda2fc4ca","f86031525725116f358b2e41325cd99a"],"dc:identifier.uri":["https://scholarbank.nus.edu.sg/bitstreams/87fd29bb-66a0-4b23-8d56-4ded5afd6601/download"],"dc:relation.isreferencedby":["https://scholarbank.nus.edu.sg/handle/10635/319598"],"dc:rights":["https://scholarbank.nus.edu.sg/bitstreams/ebe61551-59d6-4dfd-bdfd-5fa129f7a2fd/download"],"dc:subject":["Organic reaction","Ion pairing","DNA repair","Asymmetric catalysis","DNA hybrid catalyst","DNA catalysis"],"dc:title":["ENZYME-LIKE DNA CATALYST DESIGN"],"dc:type":["Thesis"]},"updated_at":"2026-07-24T03:31:13Z"}