Synthesis and Properties of (1<i>R</i>(<i>S</i>),5<i>R</i>(<i>S</i>),7<i>R</i>(<i>S</i>),8<i>R</i>(<i>S</i>))-1,8-Bis(hydroxymethyl)-6-azadispiro[4.1.4.2]tridecane-6-oxyl: Reduction-Resistant Spin Labels with High Spin Relaxation Times
Site-directed spin labeling followed by investigation using Electron Paramagnetic Resonance spectroscopy is a rapidly expanding powerful biophysical technique to study structure, local dynamics and functions of biomolecules using pulsed EPR techniques and nitroxides are the most widely used spin lab...
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MDPI AG
2023-07-01
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| Series: | International Journal of Molecular Sciences |
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| Online Access: | https://www.mdpi.com/1422-0067/24/14/11498 |
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| author | Yulia V. Khoroshunova Denis A. Morozov Danil A. Kuznetsov Tatyana V. Rybalova Yurii I. Glazachev Elena G. Bagryanskaya Igor A. Kirilyuk |
| author_facet | Yulia V. Khoroshunova Denis A. Morozov Danil A. Kuznetsov Tatyana V. Rybalova Yurii I. Glazachev Elena G. Bagryanskaya Igor A. Kirilyuk |
| author_sort | Yulia V. Khoroshunova |
| collection | DOAJ |
| description | Site-directed spin labeling followed by investigation using Electron Paramagnetic Resonance spectroscopy is a rapidly expanding powerful biophysical technique to study structure, local dynamics and functions of biomolecules using pulsed EPR techniques and nitroxides are the most widely used spin labels. Modern trends of this method include measurements directly inside a living cell, as well as measurements without deep freezing (below 70 K), which provide information that is more consistent with the behavior of the molecules under study in natural conditions. Such studies require nitroxides, which are resistant to the action of biogenic reductants and have high spin relaxation (dephasing) times, T<sub>m</sub>. (1<i>R</i>(<i>S</i>),5<i>R</i>(<i>S</i>),7<i>R</i>(<i>S</i>),8<i>R</i>(<i>S</i>))-1,8-bis(hydroxymethyl)-6-azadispiro[4.1.4.2]tridecane-6-oxyl is a unique nitroxide that combines these features. We have developed a convenient method for the synthesis of this radical and studied the ways of its functionalization. Promising spin labels have been obtained, the parameters of their spin relaxation T<sub>1</sub> and T<sub>m</sub> have been measured, and the kinetics of reduction with ascorbate have been studied. |
| first_indexed | 2024-03-11T01:00:17Z |
| format | Article |
| id | doaj.art-0c64ed62cc794604a41d1d3be3263788 |
| institution | Directory Open Access Journal |
| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-11T01:00:17Z |
| publishDate | 2023-07-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | International Journal of Molecular Sciences |
| spelling | doaj.art-0c64ed62cc794604a41d1d3be32637882023-11-18T19:40:25ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672023-07-0124141149810.3390/ijms241411498Synthesis and Properties of (1<i>R</i>(<i>S</i>),5<i>R</i>(<i>S</i>),7<i>R</i>(<i>S</i>),8<i>R</i>(<i>S</i>))-1,8-Bis(hydroxymethyl)-6-azadispiro[4.1.4.2]tridecane-6-oxyl: Reduction-Resistant Spin Labels with High Spin Relaxation TimesYulia V. Khoroshunova0Denis A. Morozov1Danil A. Kuznetsov2Tatyana V. Rybalova3Yurii I. Glazachev4Elena G. Bagryanskaya5Igor A. Kirilyuk6N.N. Vorozhtsov Institute of Organic Chemistry SB RAS, Academician Lavrentiev Ave. 9, 630090 Novosibirsk, RussiaN.N. Vorozhtsov Institute of Organic Chemistry SB RAS, Academician Lavrentiev Ave. 9, 630090 Novosibirsk, RussiaDepartment of Physics, Novosibirsk State University, Pirogova Str. 1, 630090 Novosibirsk, RussiaN.N. Vorozhtsov Institute of Organic Chemistry SB RAS, Academician Lavrentiev Ave. 9, 630090 Novosibirsk, RussiaVoevodsky Institute of Chemical Kinetics and Combustion SB RAS, Institutskaya 3, 630090 Novosibirsk, RussiaN.N. Vorozhtsov Institute of Organic Chemistry SB RAS, Academician Lavrentiev Ave. 9, 630090 Novosibirsk, RussiaN.N. Vorozhtsov Institute of Organic Chemistry SB RAS, Academician Lavrentiev Ave. 9, 630090 Novosibirsk, RussiaSite-directed spin labeling followed by investigation using Electron Paramagnetic Resonance spectroscopy is a rapidly expanding powerful biophysical technique to study structure, local dynamics and functions of biomolecules using pulsed EPR techniques and nitroxides are the most widely used spin labels. Modern trends of this method include measurements directly inside a living cell, as well as measurements without deep freezing (below 70 K), which provide information that is more consistent with the behavior of the molecules under study in natural conditions. Such studies require nitroxides, which are resistant to the action of biogenic reductants and have high spin relaxation (dephasing) times, T<sub>m</sub>. (1<i>R</i>(<i>S</i>),5<i>R</i>(<i>S</i>),7<i>R</i>(<i>S</i>),8<i>R</i>(<i>S</i>))-1,8-bis(hydroxymethyl)-6-azadispiro[4.1.4.2]tridecane-6-oxyl is a unique nitroxide that combines these features. We have developed a convenient method for the synthesis of this radical and studied the ways of its functionalization. Promising spin labels have been obtained, the parameters of their spin relaxation T<sub>1</sub> and T<sub>m</sub> have been measured, and the kinetics of reduction with ascorbate have been studied.https://www.mdpi.com/1422-0067/24/14/11498dispiro[pyrrolidine-2,1′-cyclopentane-5,1″-cyclopentane]6-azadispiro[4.1.4.2]tridecanenitrones1,3-dipolar cycloadditionpyrrolidine nitroxidessterically shielded nitroxides |
| spellingShingle | Yulia V. Khoroshunova Denis A. Morozov Danil A. Kuznetsov Tatyana V. Rybalova Yurii I. Glazachev Elena G. Bagryanskaya Igor A. Kirilyuk Synthesis and Properties of (1<i>R</i>(<i>S</i>),5<i>R</i>(<i>S</i>),7<i>R</i>(<i>S</i>),8<i>R</i>(<i>S</i>))-1,8-Bis(hydroxymethyl)-6-azadispiro[4.1.4.2]tridecane-6-oxyl: Reduction-Resistant Spin Labels with High Spin Relaxation Times International Journal of Molecular Sciences dispiro[pyrrolidine-2,1′-cyclopentane-5,1″-cyclopentane] 6-azadispiro[4.1.4.2]tridecane nitrones 1,3-dipolar cycloaddition pyrrolidine nitroxides sterically shielded nitroxides |
| title | Synthesis and Properties of (1<i>R</i>(<i>S</i>),5<i>R</i>(<i>S</i>),7<i>R</i>(<i>S</i>),8<i>R</i>(<i>S</i>))-1,8-Bis(hydroxymethyl)-6-azadispiro[4.1.4.2]tridecane-6-oxyl: Reduction-Resistant Spin Labels with High Spin Relaxation Times |
| title_full | Synthesis and Properties of (1<i>R</i>(<i>S</i>),5<i>R</i>(<i>S</i>),7<i>R</i>(<i>S</i>),8<i>R</i>(<i>S</i>))-1,8-Bis(hydroxymethyl)-6-azadispiro[4.1.4.2]tridecane-6-oxyl: Reduction-Resistant Spin Labels with High Spin Relaxation Times |
| title_fullStr | Synthesis and Properties of (1<i>R</i>(<i>S</i>),5<i>R</i>(<i>S</i>),7<i>R</i>(<i>S</i>),8<i>R</i>(<i>S</i>))-1,8-Bis(hydroxymethyl)-6-azadispiro[4.1.4.2]tridecane-6-oxyl: Reduction-Resistant Spin Labels with High Spin Relaxation Times |
| title_full_unstemmed | Synthesis and Properties of (1<i>R</i>(<i>S</i>),5<i>R</i>(<i>S</i>),7<i>R</i>(<i>S</i>),8<i>R</i>(<i>S</i>))-1,8-Bis(hydroxymethyl)-6-azadispiro[4.1.4.2]tridecane-6-oxyl: Reduction-Resistant Spin Labels with High Spin Relaxation Times |
| title_short | Synthesis and Properties of (1<i>R</i>(<i>S</i>),5<i>R</i>(<i>S</i>),7<i>R</i>(<i>S</i>),8<i>R</i>(<i>S</i>))-1,8-Bis(hydroxymethyl)-6-azadispiro[4.1.4.2]tridecane-6-oxyl: Reduction-Resistant Spin Labels with High Spin Relaxation Times |
| title_sort | synthesis and properties of 1 i r i i s i 5 i r i i s i 7 i r i i s i 8 i r i i s i 1 8 bis hydroxymethyl 6 azadispiro 4 1 4 2 tridecane 6 oxyl reduction resistant spin labels with high spin relaxation times |
| topic | dispiro[pyrrolidine-2,1′-cyclopentane-5,1″-cyclopentane] 6-azadispiro[4.1.4.2]tridecane nitrones 1,3-dipolar cycloaddition pyrrolidine nitroxides sterically shielded nitroxides |
| url | https://www.mdpi.com/1422-0067/24/14/11498 |
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