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.

Towards the design of a portal framework for web services integration

Web services based systems have recently found their way into many applications such as e-commerce, corporate integration and e-learning. Construction of new services or introducing new functions to existing services requires composition of web services. Current approaches to service composition often require major programming effort; this is time consuming and requires considerable developer expertise. In this paper, we explore the real and rich scenarios found in e-learning where education services are offered through the Internet by networked universities to potentially millions in the world. These services are derived from existing/emerging business operation processes and commonly offered through a web interface, combined with other services such as email and ftp services, to support partial/full business processes. We identify the requirements for a generic portal framework for easy integration of existing expertise and services of individual institutions (enterprises). We examine the existing technologies and standards, and point out the gaps to be filled in designing the architecture of the framework