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.

Using EMGs and kinematics data to study the take-off technique of experts and novices for a pole vaulting short run-up educational exercise

This study attempts to characterise the electromyographic activity and kinematics exhibited during the performance of take-off for a pole vaulting short run-up educational exercise, for different expertise levels. Two groups (experts and novices) participated in this study. Both groups were asked to execute their take-off technique for that specific exercise. Among the kinematics variables studied, the knee, hip and ankle angles and the hip and knee angular velocities were significantly different. There were also significant differences in the EMG variables, especially in terms of (i) biceps femoris and gastrocnemius lateralis activity at touchdown and (ii) vastus lateralis and gastrocnemius lateralis activity during take-off. During touchdown, the experts tended to increase the stiffness of the take-off leg to decrease braking. Novices exhibited less stiffness in the take-off leg due to their tendency to maintain a tighter knee angle. Novices also transferred less energy forward during take-off due to lack of contraction in the vastus lateralis, which is known to contribute to forward energy transfers. This study highlights the differences in both groups in terms of muscular and angular control according to the studied variables. Such studies of pole vaulting could be useful to help novices to learn expert's technique.

Fostering 'habits of reflection, independent study and free inquiry': an analysis of the short-lived phenomenon of General/Liberal Studies in English vocational education and training

In 1957, 12 years after the end of World War II, the Ministry of Education issued Circular 323 to promote the development of an element of ‘liberal studies’ in courses offered by technical and further education (FE) colleges in England. This was perceived to be in some ways a peculiar or uncharacteristic development. However, it lasted over 20 years, during which time most students on courses in FE colleges participated in what were termed General or Liberal Studies classes that complemented and/or contrasted with the technical content of their vocational programmes. By the end of the 1970s, these classes had changed in character, moving away from the concept of a ‘liberal education’ towards a prescribed diet of ‘communication studies’. The steady decline in apprenticeship numbers from the late 1960s onwards accelerated in the late 1970s, resulting in a new type of student (the state-funded ‘trainee’) into colleges whose curriculum would be prescribed by the Manpower Services Commission. This paper examines the Ministry’s thinking and charts the rise and fall of a curriculum phenomenon that became immortalised in the ‘Wilt’ novels of Tom Sharpe. The paper argues that the Ministry of Education’s concerns half a century ago are still relevant now, particularly as fresh calls are being made to raise the leaving age from compulsory education to 18, and in light of attempts in England to develop new vocational diplomas for full-time students in schools and colleges.