Titill: | Conformationally Restricted Isoindoline-Derived Spin Labels in Duplex DNA: Distances and Rotational Flexibility by Pulsed Electron-Electron Double Resonance Spectroscopy |
Höfundur: |
|
Útgáfa: | 2014-10-08 |
Tungumál: | Enska |
Umfang: | 15913-15919 |
Háskóli/Stofnun: | Háskóli Íslands University of Iceland |
Svið: | Verkfræði- og náttúruvísindasvið (HÍ) School of Engineering and Natural Sciences (UI) |
Deild: | Raunvísindadeild (HÍ) Faculty of Physical Sciences (UI) |
Birtist í: | Chemistry - A European Journal;20(48) |
ISSN: | 0947-6539 1521-3765 (eISSN) |
DOI: | 10.1002/chem.201403726 |
Efnisorð: | EPR Spectroscopy; Nucleic acids; PELDOR; DEER; Aminoxyl radical; Litrófsgreining; Kjarnsýrur |
URI: | https://hdl.handle.net/20.500.11815/1953 |
Tilvitnun:Gophane, D.B., Endeward, B., Prisner, T.F. and Sigurdsson, S.T. (2014), Conformationally Restricted Isoindoline‐Derived Spin Labels in Duplex DNA: Distances and Rotational Flexibility by Pulsed Electron–Electron Double Resonance Spectroscopy. Chem. Eur. J., 20: 15913-15919. doi:10.1002/chem.201403726
|
|
Útdráttur:Three structurally related isoindoline-derived spin labels that have different mobilities were incorporated into duplex DNA to systematically study the effect of motion on orientation-dependent pulsed electron-electron double resonance (PELDOR) measurements. To that end, a new nitroxide spin label, U-ExIm, was synthesized and incorporated into DNA oligonucleotides. U-ExIm is the first example of a conformationally unambiguous spin label for nucleic acids, in which the nitroxide N-O bond lies on the same axis as the three single bonds used to attach the otherwise rigid isoindoline- based spin label to a uridine base. Continuous-wave (CW) EPR measurements of U-ExIm confirm a very high rotational mobility of the spin label in duplex DNA relative to the structurally related spin label U-Im, which has restricted mobility due to an intramolecular hydrogen bond. The Xband CW-EPR spectra of U-ExIm can be used to identify mismatches in duplex DNA. PELDOR distance measurements between pairs of the spin labels U-Im, OxU, and U-ExIm in duplex DNA showed a strong angular dependence for U-Im, a medium dependence for OxU, and no orientation effect for U-ExIm. Thus, precise distances can be extracted from U-ExIm without having to take orientational effects into account.
|
|
Athugasemdir:Post-print (lokagerð höfundar)
|