Issue 18, 2013

Spectroscopic and theoretical investigations of adenosine 5′-diphosphate and adenosine 5′-triphosphate dianions in the gas phase

Abstract

Doubly deprotonated adenosine 5′-diphosphate ([ADP–2H]2−) and adenosine 5′-triphosphate ([ATP–2H]2−) dianions were investigated using infrared multiple photon dissociation (IR-MPD) and photoelectron spectroscopy. Vibrational spectra acquired in the X–H stretch region (X = C, N, O) and augmented by isotope-labelling were compared to density functional theory (DFT) calculations at the B3LYP/TZVPP level. This suggests that in [ATP–2H]2− the two phosphate groups adjacent to the ribose ring are preferentially deprotonated. Photoelectron spectra recorded at 4.66 and 6.42 eV photon energies revealed adiabatic detachment energies of 1.35 eV for [ADP–2H]2− and 3.35 eV for [ATP–2H]2−. Repulsive Coulomb barriers were estimated at ∼2.2 eV for [ADP–2H]2− and ∼1.9 eV for [ATP–2H]2−. Time-dependent DFT calculations have been used to simulate the photoelectron spectra. Photodetachment occurs primarily from lone pair orbitals on oxygen atoms within the phosphate chain.

Graphical abstract: Spectroscopic and theoretical investigations of adenosine 5′-diphosphate and adenosine 5′-triphosphate dianions in the gas phase

Supplementary files

Article information

Article type
Paper
Submitted
29 Oct 2012
Accepted
05 Dec 2012
First published
05 Dec 2012

Phys. Chem. Chem. Phys., 2013,15, 6640-6650

Spectroscopic and theoretical investigations of adenosine 5′-diphosphate and adenosine 5′-triphosphate dianions in the gas phase

F. Schinle, P. E. Crider, M. Vonderach, P. Weis, O. Hampe and M. M. Kappes, Phys. Chem. Chem. Phys., 2013, 15, 6640 DOI: 10.1039/C2CP43808A

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