Orientation-selective and frequency-correlated light-induced pulsed dipolar spectroscopy
We explore the potential of orientation-resolved pulsed dipolar spectroscopy (PDS) in light-induced versions of the experiment. The use of triplets as spin-active moieties for PDS offers an attractive tool for studying biochemical systems containing optically active cofactors. Cofactors are often ri...
| Main Authors: | , , , , , |
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| Format: | Journal article |
| Language: | English |
| Published: |
American Chemical Society
2021
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| _version_ | 1826279086721335296 |
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| author | Bowen, AM Bertran, A Henbest, KB Gobbo, M Timmel, CR Di Valentin, M |
| author_facet | Bowen, AM Bertran, A Henbest, KB Gobbo, M Timmel, CR Di Valentin, M |
| author_sort | Bowen, AM |
| collection | OXFORD |
| description | We explore the potential of orientation-resolved pulsed dipolar spectroscopy (PDS) in light-induced versions of the experiment. The use of triplets as spin-active moieties for PDS offers an attractive tool for studying biochemical systems containing optically active cofactors. Cofactors are often rigidly bound within the protein structure, providing an accurate positional marker. The rigidity leads to orientation selection effects in PDS, which can be analyzed to give both distance and mutual orientation information. Herein we present a comprehensive analysis of the orientation selection of a full set of light-induced PDS experiments. We exploit the complementary information provided by the different light-induced techniques to yield atomic-level structural information. For the first time, we measure a 2D frequency-correlated laser-induced magnetic dipolar spectrum, and we are able to monitor the complete orientation dependence of the system in a single experiment. Alternatively, the summed spectrum enables an orientation-independent analysis to determine the distance distribution. |
| first_indexed | 2024-03-06T23:53:34Z |
| format | Journal article |
| id | oxford-uuid:7375df8d-a02a-4dd5-995c-53e935627d13 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T23:53:34Z |
| publishDate | 2021 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | oxford-uuid:7375df8d-a02a-4dd5-995c-53e935627d132022-03-26T19:56:30ZOrientation-selective and frequency-correlated light-induced pulsed dipolar spectroscopyJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:7375df8d-a02a-4dd5-995c-53e935627d13EnglishSymplectic ElementsAmerican Chemical Society2021Bowen, AMBertran, AHenbest, KBGobbo, MTimmel, CRDi Valentin, MWe explore the potential of orientation-resolved pulsed dipolar spectroscopy (PDS) in light-induced versions of the experiment. The use of triplets as spin-active moieties for PDS offers an attractive tool for studying biochemical systems containing optically active cofactors. Cofactors are often rigidly bound within the protein structure, providing an accurate positional marker. The rigidity leads to orientation selection effects in PDS, which can be analyzed to give both distance and mutual orientation information. Herein we present a comprehensive analysis of the orientation selection of a full set of light-induced PDS experiments. We exploit the complementary information provided by the different light-induced techniques to yield atomic-level structural information. For the first time, we measure a 2D frequency-correlated laser-induced magnetic dipolar spectrum, and we are able to monitor the complete orientation dependence of the system in a single experiment. Alternatively, the summed spectrum enables an orientation-independent analysis to determine the distance distribution. |
| spellingShingle | Bowen, AM Bertran, A Henbest, KB Gobbo, M Timmel, CR Di Valentin, M Orientation-selective and frequency-correlated light-induced pulsed dipolar spectroscopy |
| title | Orientation-selective and frequency-correlated light-induced pulsed dipolar spectroscopy |
| title_full | Orientation-selective and frequency-correlated light-induced pulsed dipolar spectroscopy |
| title_fullStr | Orientation-selective and frequency-correlated light-induced pulsed dipolar spectroscopy |
| title_full_unstemmed | Orientation-selective and frequency-correlated light-induced pulsed dipolar spectroscopy |
| title_short | Orientation-selective and frequency-correlated light-induced pulsed dipolar spectroscopy |
| title_sort | orientation selective and frequency correlated light induced pulsed dipolar spectroscopy |
| work_keys_str_mv | AT bowenam orientationselectiveandfrequencycorrelatedlightinducedpulseddipolarspectroscopy AT bertrana orientationselectiveandfrequencycorrelatedlightinducedpulseddipolarspectroscopy AT henbestkb orientationselectiveandfrequencycorrelatedlightinducedpulseddipolarspectroscopy AT gobbom orientationselectiveandfrequencycorrelatedlightinducedpulseddipolarspectroscopy AT timmelcr orientationselectiveandfrequencycorrelatedlightinducedpulseddipolarspectroscopy AT divalentinm orientationselectiveandfrequencycorrelatedlightinducedpulseddipolarspectroscopy |