Can density functional theory (DFT) be used as an aid to a deeper understanding of tandem mass spectrometric fragmentation pathways?

Prediction of tandem mass spectrometric (MS/MS) fragmentation for non-peptidic molecules based on structure is of immense interest to the mass spectrometrist. If a reliable approach to MS/MS prediction could be achieved its impact within the pharmaceutical industry could be immense. Many publications have stressed that the fragmentation of a molecular ion or protonated molecule is a complex process that depends on many parameters, making prediction difficult. Commercial prediction software relies on a collection of general heuristic rules of fragmentation, which involve cleaving every bond in the structure to produce a list of 'expected' masses which can be compared with the experimental data. These approaches do not take into account the thermodynamic or molecular orbital effects that impact on the molecule at the point of protonation which could influence the potential sites of bond cleavage based on the structural motif. A series of compounds have been studied by examining the experimentally derived high-resolution MS/MS data and comparing it with the in silico modelling of the neutral and protonated structures. The effect that protonation at specific sites can have on the bond lengths has also been determined. We have calculated the thermodynamically most stable protonated species and have observed how that information can help predict the cleavage site for that ion. The data have shown that this use of in silico techniques could be a possible way to predict MS/MS spectra. Copyright (C) 2009 John Wiley & Sons, Ltd.

From Agatha Christie to Ruth Rendell: British women writers in detective and crime fiction

This work considers, seriously, the hugely popular and influential works of Agatha Christie, Dorothy L.Sayers, Margery Allingham, Ngaio Marsh, P.D. James and Ruth Rendell/Barbara Vine. Providing studies of 42 key novels, it introduces these authors for students and the general reader within the contexts of their lives, and critical debates on gender, colonialism, psychoanalysis, the Gothic, and feminism. It includes interviews with P.D. James and Ruth Rendell/Barbara Vine. [From the Publisher]

More public rescues for more private finance failures - a critique of the EC Communication on PPPs

A critique of the EC Communication on PPPs, challenging the scale of state aid offered to PPPs, the role of PPPs in the economic recovery strategy for the EU, and drawing attention to the damage done to public authorities by 'innovative' financing mechanisms.