{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"omics_type":["Unknown"],"volume":["16(48)"],"submitter":["Dolinski ND"],"pubmed_abstract":["The wide availability, ease of manipulation, and access to spatiotemporal control make light an attractive stimulus for controlling dynamic covalent chemistries/networks. In this work, a series of photo-isomerizable benzalisoxazolone (BIOx) thia-Michael (tM) acceptors were developed that exhibit an increase in thiol-bonding during irradiation with visible light (455-470 nm). <i>In situ</i> photo-NMR experiments demonstrate significant increases in the overall system <i>K</i> <sub>eq</sub> (extent of bonding) for a variety of electronically-substituted BIOx tM acceptors. A combination of experimental and computational studies show that steric interactions between the β-phenyl ring and substituent on the isoxazolone in the <i>E</i>-isomer serve as a driving force for the increased <i>K</i> <sub>eq</sub>. In addition, it is demonstrated that the power/intensity of the light can be used to tune the system's response. Incorporation of these photoisomerizable motifs into dynamic polymer networks gives access to organogels that exhibit reversible, on-demand, light-triggered stiffening."],"journal":["Chemical science"],"pagination":["23019-23025"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC12590959"],"repository":["biostudies-literature"],"pubmed_title":["Manipulating dynamic covalent bonds through direct photoisomerization."],"pmcid":["PMC12590959"],"pubmed_authors":["Snyder SA","Crolais AE","Boynton NR","Dolinski ND","Chen C","de Pablo JJ","Rowan SJ"],"additional_accession":[]},"is_claimable":false,"name":"Manipulating dynamic covalent bonds through direct photoisomerization.","description":"The wide availability, ease of manipulation, and access to spatiotemporal control make light an attractive stimulus for controlling dynamic covalent chemistries/networks. In this work, a series of photo-isomerizable benzalisoxazolone (BIOx) thia-Michael (tM) acceptors were developed that exhibit an increase in thiol-bonding during irradiation with visible light (455-470 nm). <i>In situ</i> photo-NMR experiments demonstrate significant increases in the overall system <i>K</i> <sub>eq</sub> (extent of bonding) for a variety of electronically-substituted BIOx tM acceptors. A combination of experimental and computational studies show that steric interactions between the β-phenyl ring and substituent on the isoxazolone in the <i>E</i>-isomer serve as a driving force for the increased <i>K</i> <sub>eq</sub>. In addition, it is demonstrated that the power/intensity of the light can be used to tune the system's response. Incorporation of these photoisomerizable motifs into dynamic polymer networks gives access to organogels that exhibit reversible, on-demand, light-triggered stiffening.","dates":{"release":"2025-01-01T00:00:00Z","publication":"2025 Dec","modification":"2026-06-06T01:13:26.925Z","creation":"2026-05-24T03:12:17.805Z"},"accession":"S-EPMC12590959","cross_references":{"pubmed":["41210284"],"doi":["10.1039/d5sc06704a"]}}