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Issue 18, 2013
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Spectroscopic and theoretical investigations of adenosine 5′-diphosphate and adenosine 5′-triphosphate dianions in the gas phase

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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

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Publication details

The article was received on 29 Oct 2012, accepted on 05 Dec 2012 and first published on 05 Dec 2012


Article type: Paper
DOI: 10.1039/C2CP43808A
Citation: Phys. Chem. Chem. Phys., 2013,15, 6640-6650
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    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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