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.

Peat, pine stumps and people: interactions behind climate, vegetation change and human activity in wetland archaeology at Loch Farlary, Northern Scotland

First paragraph: In 1993, a peat-cutter, Bruce Field, working on the blanket peat bank he rented from the Sutherland Estate by Loch Farlary, above Golspie in Sutherland (fig 1), reported to Scottish Natural Heritage and Historic Scotland several pieces of pine wood bearing axe marks. Their depth in the peat suggested the cut marks to be prehistoric. This paper summarizes the work undertaken to understand the age and archaeological significance of this find (see also Tipping et al 2001 in press). The pine trees were initially thought to be part of a population that flourished briefly across northern Scotland in the middle of the Holocene period from c 4800 cal BP (Huntley, Daniell & Allen 1997). The subsequent collapse across northernmost Scotland of this population, the pine decline, at around 4200-4000 cal BP is unexplained: climate change has been widely assumed (Dubois & Ferguson 1985; Bridge, Haggart & Lowe 1990; Gear & Huntley 1991) but anthropogenic activity has not been disproved (Birks 1975; Bennett 1995). It was hypothesized that the Farlary find would allow for the first time the direct link between human woodland clearance and the Early Bronze Age pine decline.