Hansen, DF;
(2017)
Measurement of (15)N longitudinal relaxation rates in (15)NH4(+) spin systems to characterise rotational correlation times and chemical exchange.
Journal of Magnetic Resonance
, 279
pp. 91-98.
10.1016/j.jmr.2017.01.015.
Preview |
Text
1-s2.0-S109078071730023X-main.pdf - Published Version Download (828kB) | Preview |
Abstract
Many chemical and biological processes rely on the movement of monovalent cations and an understanding of such processes can therefore only be achieved by characterising the dynamics of the involved ions. It has recently been shown that (15)N-ammonium can be used as a proxy for potassium to probe potassium binding in bio-molecules such as DNA quadruplexes and enzymes. Moreover, equations have been derived to describe the time-evolution of (15)N-based spin density operator elements of (15)NH4(+) spin systems. Herein NMR pulse sequences are derived to select specific spin density matrix elements of the (15)NH4(+) spin system and to measure their longitudinal relaxation in order to characterise the rotational correlation time of the (15)NH4(+) ion as well as report on chemical exchange events of the (15)NH4(+) ion. Applications to (15)NH4(+) in acidic aqueous solutions are used to cross-validate the developed pulse sequence while measurements of spin-relaxation rates of (15)NH4(+) bound to a 41kDa domain of the bacterial Hsp70 homologue DnaK are presented to show the general applicability of the derived pulse sequence. The rotational correlation time obtained for (15)N-ammonium bound to DnaK is similar to the correlation time that describes the rotation about the threefold axis of a methyl group. The methodology presented here provides, together with the previous theoretical framework, an important step towards characterising the motional properties of cations in macromolecular systems.
| Type: | Article |
|---|---|
| Title: | Measurement of (15)N longitudinal relaxation rates in (15)NH4(+) spin systems to characterise rotational correlation times and chemical exchange. |
| Location: | United States |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1016/j.jmr.2017.01.015 |
| Publisher version: | http://dx.doi.org/10.1016/j.jmr.2017.01.015 |
| Language: | English |
| Additional information: | © 2017 The Authors. Published by Elsevier Inc. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/). |
| Keywords: | AX(4) spin systems, Ammonium, Chemical exchange, NMR, Nuclear spin relaxation |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > School of Life and Medical Sciences UCL > Provost and Vice Provost Offices > School of Life and Medical Sciences > Faculty of Life Sciences UCL > Provost and Vice Provost Offices > School of Life and Medical Sciences > Faculty of Life Sciences > Div of Biosciences UCL > Provost and Vice Provost Offices > School of Life and Medical Sciences > Faculty of Life Sciences > Div of Biosciences > Structural and Molecular Biology |
| URI: | https://discovery.ucl.ac.uk/id/eprint/1559192 |
Archive Staff Only
 |
View Item |
