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1.
Phys Chem Chem Phys ; 16(40): 21980-7, 2014 Oct 28.
Artículo en Inglés | MEDLINE | ID: mdl-25205444

RESUMEN

We report experimental total, absolute, fragmentation cross sections for anthracene C14H10, acridine C13H9N, and phenazine C12H8N2 ions colliding with He at center-of-mass energies close to 100 eV. In addition, we report results for the same ions colliding with Ne, Ar, and Xe at higher energies. The total fragmentation cross sections for these three ions are the same within error bars for a given target. The measured fragment mass distributions reveal significant contributions from both delayed (≫10(-12) s) statistical fragmentation processes as well as non-statistical, prompt (∼10(-15) s), single atom knockout processes. The latter dominate and are often followed by secondary statistical fragmentation. Classical Molecular Dynamics (MD) simulations yield separate cross sections for prompt and delayed fragmentation which are consistent with the experimental results. The intensity of the single C/N-loss peak, the signature of non-statistical fragmentation, decreases with the number of N atoms in the parent ion. The fragment intensity distributions for losses of more than one C or N atom are rather similar for C14H10 and C13H9N but differ strongly for C12H8N2 where weak C-N bonds often remain in the fragments after the first fragmentation step. This greatly increases their probability to fragment further. Distributions of internal energy remaining in the fragments after knockout are obtained from the MD simulations.

2.
J Am Soc Mass Spectrom ; 28(12): 2686-2691, 2017 12.
Artículo en Inglés | MEDLINE | ID: mdl-28936701

RESUMEN

Here we report on the gas-phase interactions between protonated enantiopure amino acids (L- and D-enantiomers of Met, Phe, and Trp) and chiral target gases [(R)- and (S)-2-butanol, and (S)-1-phenylethanol] in 0.1-10.0 eV low-energy collisions. Two major processes are seen to occur over this collision energy regime, collision-induced dissociation and ion-molecule complex formation. Both processes were found to be independent of the stereo-chemical composition of the interacting ions and targets. These data shed light on the currently debated mechanisms of gas-phase chiral selectivity by demonstrating the inapplicability of the three-point model to these interactions, at least under single collision conditions. Graphical Abstract.


Asunto(s)
Aminoácidos/química , Protones , Butanoles/química , Gases/química , Metionina/química , Modelos Moleculares , Fenilalanina/química , Alcohol Feniletílico/química , Estereoisomerismo , Espectrometría de Masas en Tándem , Termodinámica , Triptófano/química
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