Journal Article

PUBDB-2024-04728

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png How Does $Mg^{2+}_{(aq)}$ Interact with $ATP_{(aq)}$? Biomolecular Structure through the Lens of Liquid-Jet Photoemission Spectroscopy

Mudryk, K.Extern* ; Lee, C.Extern* ; Tomaník, L. ; Malerz, S.Extern* ; Trinter, F.Extern*XFEL.EU* ; Hergenhahn, U.Extern* ; Neumark, D. M. ; Slavicek, P. (Corresponding author)Extern*XFEL.EU* ; Bradforth, S. (Corresponding author) ; Winter, B. (Corresponding author)Extern*

2024
ACS Publications Washington, DC

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Please use a persistent id in citations: doi:10.1021/jacs.4c03174  doi:10.3204/PUBDB-2024-04728

Abstract: Liquid-jet photoemission spectroscopy (LJ-PES) allows for a direct probing of electronic structure in aqueous solutions. We show the applicability of the approach to biomolecules in a complex environment, exploring site-specific information on the interaction of adenosine triphosphate in the aqueous phase (ATP$_{(aq)}$) with magnesium (Mg$^{2+}$$_{(aq)}$), highlighting the synergy brought about by the simultaneous analysis of different regions in the photoelectron spectrum. In particular, we demonstrate intermolecular Coulombic decay (ICD) spectroscopy as a new and powerful addition to the arsenal of techniques for biomolecular structure investigation. We apply LJ-PES assisted by electronic-structure calculations to study ATP$_{(aq)}$ solutions with and without dissolved Mg$^{2+}$. Valence photoelectron data reveal spectral changes in the phosphate and adenine features of ATP$_{(aq)}$ due to interactions with the divalent cation. Chemical shifts in Mg $\small2$$p$, Mg $\small2$$s$, P $\small2$$p$, and P $\small2$$s$ core-level spectra as a function of the Mg$^{2+}$/ATP concentration ratio are correlated to the formation of [Mg(ATP) $_{2}$$]$$^{6-}$$_{(aq)}$, [MgATP]$^{2-}$$_{(aq)}$, and [Mg$_{2}$ATP]$_{(aq)}$ complexes, demonstrating the element sensitivity of the technique to Mg$^{2+}$–phosphate interactions. The most direct probe of the intermolecular interactions between ATP$_{(aq)}$ and Mg$^{2+}$$_{(aq)}$ is delivered by the emerging ICD electrons following ionization of Mg $\small1$$s$ electrons. ICD spectra are shown to sensitively probe ligand exchange in the Mg$^{2+}$–ATP$_{(aq)}$ coordination environment. In addition, we report and compare P $\small2$$s$ data from ATP$_{(aq)}$ and adenosine mono- and diphosphate (AMP$_{(aq)}$ and ADP$_{(aq)}$, respectively) solutions, probing the electronic structure of the phosphate chain and the local environment of individual phosphate units in ATP$_{(aq)}$. Our results provide a comprehensive view of the electronic structure of ATP$_{(aq)}$ and Mg$^{2+}$–ATP$_{(aq)}$ complexes relevant to phosphorylation and dephosphorylation reactions that are central to bioenergetics in living organisms.

Note: Open Access

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Contributing Institute(s):

1. DOOR-User (DOOR ; HAS-User)
2. Experimentebetreuung PETRA III (FS-PET-S)

Research Program(s):

1. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)
2. AQUACHIRAL - Chiral aqueous-phase chemistry (883759) (883759)
3. DFG project G:(GEPRIS)509471550 - Dynamik photoionisations-induzierter Prozesse in laser-präparierten Molekülen in der Gasphase und der wässrigen Phase (509471550) (509471550)
4. FS-Proposal: II-20180012 (II-20180012) (II-20180012)
5. FS-Proposal: I-20200682 (I-20200682) (I-20200682)

Experiment(s):

1. PETRA Beamline P04 (PETRA III)

Appears in the scientific report 2024

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Database coverage:
; ; ; BIOSIS Previews ; Biological Abstracts ; Chemical Reactions ; Clarivate Analytics Master Journal List ; Current Contents - Life Sciences ; Current Contents - Physical, Chemical and Earth Sciences ; Ebsco Academic Search ; Essential Science Indicators ; IF >= 15 ; Index Chemicus ; JCR ; Nationallizenz ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

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