Magnesium(II)-ATP Complexes in 1-Ethyl-3-Methylimidazolium Acetate Solutions Characterized by 31 Mg β-Radiation-Detected NMR Spectroscopy

Ryan M L McFadden; Dániel Szunyogh; Nicholas Bravo-Frank; Aris Chatzichristos; Martin H Dehn; Derek Fujimoto; Attila Jancsó; Silke Johannsen; Ildikó Kálomista; Victoria L Karner; Robert F Kiefl; Flemming H Larsen; Jens Lassen; C D Philip Levy; Ruohong Li; Iain McKenzie; Hannah McPhee; Gerald D Morris; Matthew R Pearson; Stephan P A Sauer; Roland K O Sigel; Peter W Thulstrup; W Andrew MacFarlane; Lars Hemmingsen; Monika Stachura

doi:10.1002/anie.202207137

Magnesium(II)-ATP Complexes in 1-Ethyl-3-Methylimidazolium Acetate Solutions Characterized by ³¹ Mg β-Radiation-Detected NMR Spectroscopy

Angew Chem Int Ed Engl. 2022 Aug 26;61(35):e202207137. doi: 10.1002/anie.202207137. Epub 2022 Jul 14.

Authors

Ryan M L McFadden¹, Dániel Szunyogh², Nicholas Bravo-Frank³, Aris Chatzichristos^{4

5}, Martin H Dehn^{4

5}, Derek Fujimoto^{4

5}, Attila Jancsó⁶, Silke Johannsen⁷, Ildikó Kálomista², Victoria L Karner^{5

8}, Robert F Kiefl^{1

4

5}, Flemming H Larsen⁹, Jens Lassen^{1

10

11}, C D Philip Levy¹, Ruohong Li¹, Iain McKenzie^{1

12

13}, Hannah McPhee¹⁴, Gerald D Morris¹, Matthew R Pearson¹, Stephan P A Sauer², Roland K O Sigel⁷, Peter W Thulstrup², W Andrew MacFarlane^{1

4

8}, Lars Hemmingsen², Monika Stachura^{1

12}

Affiliations

¹ TRIUMF, 4004 Wesbrook Mall, Vancouver, BC V6T 2A3, Canada.
² Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen, Denmark.
³ Faculty of Engineering, University of Victoria, 3800 Finnerty Road, Victoria, BC V8P 5C2, Canada.
⁴ Department of Physics and Astronomy, University of British Columbia, 6224 Agricultural Road, Vancouver, BC V6T 1Z1, Canada.
⁵ Stewart Blusson Quantum Matter Institute, University of British Columbia, 2355 East Mall, Vancouver, BC V6T 1Z4, Canada.
⁶ Department of Inorganic and Analytical Chemistry, University of Szeged, Dóm tér 7, 6720, Szeged, Hungary.
⁷ Department of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057, Zürich, Switzerland.
⁸ Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1, Canada.
⁹ Department of Food Science, University of Copenhagen, Rolighedsvej 26, 1958, Frederiksberg, Denmark.
¹⁰ Department of Physics, Simon Fraser University, 8888 University Drive, Burnaby, BC V5A 1S6, Canada.
¹¹ Department of Physics and Astronomy, University of Manitoba, 30A Sifton Road, Winnipeg, MB R3T 2N2, Canada.
¹² Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, BC V5A 1S6, Canada.
¹³ Department of Physics and Astronomy, University of Waterloo, 200 University Avenue West, Waterloo, ON N2L 3G1, Canada.
¹⁴ Department of Engineering, McMaster University, 1280 Main Street West, Hamilton, ON L8S 4L7, Canada.

Abstract

The complexation of Mg^II with adenosine 5'-triphosphate (ATP) is omnipresent in biochemical energy conversion, but is difficult to interrogate directly. Here we use the spin- $1 / 2$ β-emitter ³¹ Mg to study Mg^II -ATP complexation in 1-ethyl-3-methylimidazolium acetate (EMIM-Ac) solutions using β-radiation-detected nuclear magnetic resonance (β-NMR). We demonstrate that (nuclear) spin-polarized ³¹ Mg, following ion-implantation from an accelerator beamline into EMIM-Ac, binds to ATP within its radioactive lifetime before depolarizing. The evolution of the spectra with solute concentration indicates that the implanted ³¹ Mg initially bind to the solvent acetate anions, whereafter they undergo dynamic exchange and form either a mono- (³¹ Mg-ATP) or di-nuclear (³¹ MgMg-ATP) complex. The chemical shift of ³¹ Mg-ATP is observed up-field of ³¹ MgMg-ATP, in accord with quantum chemical calculations. These observations constitute a crucial advance towards using β-NMR to probe chemistry and biochemistry in solution.

Keywords: Coordination Modes; Ionic Liquids; Magnesium; NMR Spectroscopy; Nucleosides; Radiochemistry.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Adenosine Triphosphate* / chemistry
Imidazoles
Magnesium*
Magnetic Resonance Spectroscopy / methods

Substances

Imidazoles
Adenosine Triphosphate
Magnesium
1-ethyl-3-methylimidazolium