A test of the concept of ‘charge localisation’ in methionine

A previous re-investigation of methionine has shown that the [C₂H₅S]⁺ ion is generated via rather complicated routes from the molecular ion. This has been interpreted as evidence against charge localisation in the fragmentation of the title compound. Deuterium labelling, high resolution mass measurements and metastable transitions have revealed, however, that the formation of the [C₂H₅S]⁺ ion is not in contradiction with the predicting capabilities of the concept of charge localisation.     

Collisional activation spectra of the [C9H11O]+ ion from 2-methyl-2-phenylpropane-1,3-diol

Collisional activation spectra show that the [C₉H₁₁O] ion formed by loss of CH₂OH from the title compound has rearranged to the protonated phenylacetone structure.     

The problem of the azatropylium ion: Hydrogen elimination from the molecular ion of γ-picoline

Comparison of the mass spectrum of γ-picoline with that of analogues, specifically deuterated in the methyl group, the ring or both, has shown that the molecular ion loses the α,β and methyl hydrogen atoms (ω-hydrogen') in the ratio 1.43: 1: 1. 13. The same trend is found for the elimination of HCN from the molecular ion. Moreover, a value of 1.52 is found for the isotope effect, expressing the favoured loss of H over D, irrespective of its position.     

Anomalous long-range propagation of femtosecond laser pulses through air: moving focus or pulse self-guiding?

Self-guided propagation of femtosecond laser pulses is studied for a converging-beam configuration. Channeling of the pulse energy through various gases is observed over distances well beyond the lens focal point, a fact that cannot be explained by the moving-focus model. The results are in good agreement with three-dimensional numerical simulations.     

Ultrafast structural dynamics of water induced by dissipation of vibrational energy

In the liquid phase, water molecules form a disordered fluctuating network of intermolecular hydrogen bonds. Using both inter- and intramolecular vibrations as structural probes in ultrafast infrared spectroscopy, we demonstrate a two-stage structural response of this network to energy disposal: vibrational energy from individually excited water molecules is transferred to intermolecular modes, resulting in a sub-100 fs nuclear rearrangement that leaves the local hydrogen bonds weakened but unbroken. Subsequent energy delocalization over many molecules occurs on an approximately 1 ps time scale and is connected with the breaking of hydrogen bonds, resulting in a macroscopically heated liquid.     

Characterization of Hydrogen-Bonded Supramolecular Assemblies by MALDI-TOF Mass Spectrometry after Ag+ Labeling

The high affinity of Ag ⁺ ions for aromatic π donors and cyano groups is exploited in a novel MALDI-TOF mass spectrometric method for the identification of hydrogen-bonded assemblies. The interaction with the Ag⁺ ions—which, for example, can be complexed by two phenyl groups in a sandwich-type manner (see drawing on the right)—provides positively charged assemblies in a nondestructive way.     

Electron ionization induced metastable decompositions of isomeric trimethylsilylmethanol, (CH3)3SiCH2OH, and methoxytrimethylsilane, (CH3)3SiOCH3

The metastable decompositions of trimethylsilylmethanol, (CH₃)₃SiCH₂OH (MW: 104, 1) and methoxytrimethylsilane, (CH₃)₃SiOCH₃ (MW: 104, 2) upon electron ionization have been investigated by use of mass-analyzed ion kinetic energy (MIKE) spectroscopy and D labeling. The metastable ions of 1 ^·+ decompose to give the fragment ions m/z 89 (CH ₃ ^· loss) and 73 (^·CH₂OH loss), whereas those of 2 ^·+ only yield the fragment ion m/z 89 (CH ₃ ^· loss). The latter fragment ion is generated by loss of a methyl radical from the trimethylsilyl group via a simple cleavage reaction as shown by D labeling. However, the fragment ions m/z 89 and 73 from 1 ^·+ are generated following an almost statistical exchange of the original methyl and methylene hydrogen atoms in the molecular ion as shown also by D labeling. This exchange indicates a complex rearrangement of the molecular ion of 1 ^·+ prior to metastable decomposition for which as key step a 1,2-trimethylsilyl group migration from carbon to oxygen is suggested. A different behavior is also found between the source-generated m/z 89 ions from 1 ^·+ which decompose in the metastable time region to give ions m/z 61 by loss of ethylene and those from 2 ^·+ which decompose in the metastable region to yield ions m/z 59 by elimination of formaldehyde.     

Chemical ionization of phenyl n-propyl ether and methyl substituted analogs: Propene loss initiated by competing proton transfer to the oxygen atom and the aromatic ring

The mechanism of propene loss from protonated phenyl n-propyl ether and a series of mono-, di-, and trimethylphenyl n-propyl ethers has been examined by chemical ionization (CI) mass spectrometry in combination with tandem mass spectrometry experiments. The role of initial proton transfer to the oxygen atom and the aromatic ring, respectively, has been probed with the use of deuterated CI reagents, D₂O, CD₃OD, and CD₃CN (given in order of increasing proton affinity), in combination with deuterium labeling of the β position of the n-propyl group or the phenyl ring. The metastable [M + D]⁺ ions of phenyl n-propyl ether—formed with D₂O as the CI reagent—eliminate C₃H₅D and C₃H₆ in a ratio of 10:90, which indicates that the added deuteron is incorporated to a minor extent in the expelled neutral species. In the experiments with CD₃OD as the CI reagent, the ratio between the losses of C₃H₅D and C₃H₆ from the metastable [M + D]⁺ ions of phenyl n-propyl ether is 18:82, whereas the ratio becomes 27:73 with CD₃CN as the reagent. A similar trend in the tendency to expel a propene molecule that contains the added deuteron is observed for the metastable [M + D]⁺ ions of phenyl n-propyl ether labeled at the β position of the alkyl group. Incorporation of a hydrogen atom that originates from the aromatic ring in the expelled propene molecule is of negligible importance as revealed by the minor loss of C₃H₅D from the metastable [M + H]⁺ ions of C₆D₅OCH₂CH₂CH₃ irrespective of whether H₂O, CH₃OH, or CH₃CN is the CI reagent. The combined results for the [M + D]⁺ ions of phenyl n-propyl ether and deuterium-labeled analogs are suggested to be in line with a model that assumes that propene loss occurs not only from species formed by deuteron transfer to the oxygen atom, but also from ions generated by deuteron transfer to the ring. This is substantiated by the results for the methyl-substituted ethers, which reveal that the position as well as the number of methyl groups bonded to the ring exert a marked effect on the relative importances of the losses of C₃H₅D and C₃H₆ from the metastable [M + D]⁺ ions of the unlabeled methyl-substituted species.