Imaging with mass spectrometry.

Novel graph theoretical approach to heteroatoms in quantitative structure—activity relationships

Gas-phase dissociation reactions of protonated amino acidsphenylalanine, tyrosine, tryptophan, and histidineare rich and diverse. Considerable similarities exist among the four amino acids, but there are also significant differences. Facile reactions include the elimination of NH3, common to all aromatic amino acids except histidine, and the concomitant elimination of H2O and CO. Labeling experiments with deuteriums show considerable H/D scrambling prior to dissociation involving N−H, O−H, and C−H (both aliphatic and aromatic hydrogens). Mechanisms of this scrambling are proposed. At higher collision energies, eliminations of H2O, CO, CO2, and CH2CO occur after that of NH3. Similarly, eliminations of HCN, HCNH2, and NH3 occur after that of H2O and CO. The elimination of CH2CO is preceded by migration of the hydroxyl ion from the carboxylic group to the exocyclic carbon on the side chain. Aromatic amino acids, with the exception of tyrosine, were observed to yield cationic radical fragments by eliminating ...

Gas-Phase Fragmentation Reactions of Protonated Aromatic Amino Acids: Concomitant and Consecutive Neutral Eliminations and Radical Cation Formations

A molecular descriptor based upon a count statistic of the topological distance matrix is described and evaluated for use in QSAR studies. Encoding a molecule is done by computing many selective count statistics (histograms) reflecting the distribution of different atom types and bond types in the molecule. The descriptor was also extended to incorporate geometric features of molecules by weighting the topological distance counts with the geometric distance. It is invariant to both translation and rotation. As a result, it does not require the alignment of the structures under study. The method was applied to several QSAR data sets and performed equally well or better than CoMFA and the EVA descriptor. Compared to the latter two methods, it is computationally easier.

Steven. Steiner

Papers

Direct-linked gas chromatography-Fourier transform infrared-mass spectrometer system

A graph-theoretic approach to quantitative structure—activity/reactivity studies