VUV Photoionization and Dissociation of Tyramine and Dopamine: the Joint Experimental and Theoretical Studies |
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Authors: | Hui-jun Guo Li-li Ye Liang-yuan Jia Li-dong Zhang Fei Qi |
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Institution: | National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, China |
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Abstract: | Photon induced dissociation investigations of neutral tyramine and dopamine are carried out with synchrotron vacuum ultraviolet photoionization mass spectrometry and theoretical calculations. At low photon energy, only molecular ions are measured by virtue of near-threshold photoionization. While increasing photon energy to 11.7 eV or more, four distinct fragment ions are obtained for tyramine and dopamine, respectively. Besides, the ioniza-tion energies of tyramine and dopamine are determined to be 7.98±0.05 and 7.67±0.05 eV by measuring the photoionization efficiency curves of corresponding molecular ions. With help of density function theory calculations, the detailed fragmentation pathways are es-tablished as well. These two molecular cations have similar aminoethyl group elimination pathways, C7H8O2+·(m/z=124) and C7H8O+·(m/z=108) are supposed to be generated by the McLafferty rearrangement via γ-hydrogen (γ-H) shift inducing β-fission. And CH2NH2+ is proposed to derive from the direct fission of C7-C8 bond. Besides, the McLafferty rear-rangement and the C7-C8 bond fission are validated to be dominant dissociation pathways for tyramine and dopamine cations. |
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Keywords: | Tyramine Dopamine VUV photoionization Mass spectrometry Ionization energy Dissociation pathway |
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