Gas Phase Bond Formation in Dipeptide Clusters.

Protein bonds between amino acids are one of the most important biological linkages that create life. The detection of amino acids in the interstellar environments and in meteorites may lead to the suggestion that amino acids came from outer space and that peptides bonds may have been created in the gas phase. Here we show experimentally the creation of covalent bonds, most likely peptide bonds, between serine dipeptides in the gas phase. More specifically, we show that spraying a solution of Ser-Ser dipeptides results, in addition to dipeptide clusters, in a peak with the same mass as the serine tetrapeptide, which also has the same fragmentation pattern. Moreover, we show that this mass is formed upon collision induced dissociation of clusters containing four serine dipeptides. Thence, if the dipeptide can be generated abiotically the polymerization process may occur spontaneously.

Harmonic height distribution in pickup spectroscopy within electrostatic ion beam traps.

Pickup spectroscopy is a means of determining the abundance, mass, charge, and lifetime of ions oscillating in electrostatic ion beam traps. Here, we present a framework for describing the harmonic height distribution of the Fourier transform of the pickup signal and discuss the importance of the pickup positioning, bunch dynamics, and pickup width on the harmonic height distribution. We demonstrate the methodology using measurements from a newly constructed electrostatic ion beam trap.

Clusters of betaine with positive and negative ions: Evidence for the betaine tetramer being magic.

Betaine (Bet) is a pure zwitterion with an extraordinarily large dipole moment, which allows it to form stable clusters in the gas phase of the form X±BetN, where X± is a positive or negative ion. We show here that such clusters have a prominent magic number at N = 4 for all X± ions used in this work. Nevertheless, we observe a marked difference in the fragmentation pattern of anionic and cationic clusters: while cationic clusters fragment by evaporating one betaine monomer at a time, fragmentation of anionic clusters is through fission resulting in the emission of one or several betaine molecules. Theoretical calculations show that charged betaine tetramers have a square like structure with the central ion lying above the cluster plane and explain the difference in fragmentation patterns as a result of the charge distribution within the betaine molecule.

Isotope Labeling Study of Retinal Chromophore Fragmentation.

Previous studies have shown that the gas-phase fragmentation of the retinal chromophore after S0-S1 photoexcitation results in a prominent fragment of mass 248 which cannot be explained by the cleavage of any single bond along the polyene chain. It was therefore theorized that the fragmentation mechanism involves a series of isomerizations and cyclization processes, and two mechanisms for these processes were suggested. Here we used isotope labeling MS-MS to provide conclusive support for the fragmentation mechanism suggested by Coughlan et al. (J. Phys. Chem. Lett. 2014, 5, 3195).