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.

A new species of Tortanus (Atortus)(Copepoda: Calanoida: Tortanidae) from Rodrigues Island, Mauritius

A new species of the copepod genus Tortanus (Atortus) (Copepoda: Calanoida), T. (A.) insularis, is described from the coastal region of Rodrigues Island, Mauritius, an isolated island in the south-western Indian Ocean. This new species can be assigned to an Indian element, the recticauda species group, in the Indo-West Pacific recticauda species complex. It exhibits the closest relationship to T. (A.) recticauda recorded from the southern Red Sea and Arabian Gulf, rather than the more closely distributed T. (A.) capensis, recorded from off South Africa.

Effect of habitat fragmentation on the macroinvertebrate infaunal communities associated with the seagrass Zostera marina

1. The effect of habitat fragmentation was investigated in two adjacent, yet separate, intertidal Zostera marina beds in the Salcombe Estuary, Devon, UK. The seagrass bed on the west bank comprised a continuous meadow of ca. 2.3 ha, whilst the bed on the east bank of the estuary was fragmented into patches of 6–9 m2.2. Three 10 cm diameter core samples for infaunal macroinvertebrates were taken from three stations within each bed. No significant difference was found in univariate community parameters between beds, or in measured seagrass parameters. However, multivariate analysis revealed a significant difference in community composition, due mainly to small changes in species abundance rather than differences in the species present.3. The species contributing most to the dissimilarity between the two communities were polychaetes generally associated with unvegetated habitats (e.g. Magelona mirabilis) and found to be more common in the fragmented bed.4. A significant difference in median grain size and sorting coefficient was recorded between the two beds, and median grain size was found to be the variable best explaining multivariate community patterns.5. The results of the study provide evidence for the effects of habitat fragmentation on the communities associated with seagrass beds, habitats which are of high conservation importance. As the infaunal community is perhaps intuitively the component least likely to be affected by fragmentation at the scale observed, the significant difference in community composition recorded has consequences for more sensitive and high-profile parts of the biota (e.g. fish), and thus for the conservation of seagrass habitats and their associated communities.

Island-coastal and oceanic epipelagic zooplankton biodiversity in the southwestern Indian Ocean

The oceanic Indian Ocean zooplankton species and their distributions have been well described, but the zooplankton of coastal regions, particularly around the oceanic islands, has not been well researched, either taxonomically or experimentally. The environment of the Mascarene region in the southwestern Indian Ocean and zooplankton research that has been carried out there is detailed, along with gaps in our knowledge. Suggestions are given for future research, particularly on the zooplankton species adapted to live in the fluctuating environment of inshore waters, including studies on taxonomy and biodiversity, life cycles, dispersion and genetics. Problems of carrying out taxonomic research are highlighted.

Phytogeographic characterization of Gran Canaria Island (Canary Islands-Spain)

Studies on the flora and fauna of the Canary Islands show that this Archipelago is one of the planet’s diversity hot spots. However, an analysis of the differences in the phytogeographic characteristics of each of the islands that make up this Archipelago is lacking. This article focuses on the phytogeographic characterization of the island of Gran Canaria. This island exhibits geological and climatic characteristics resulting in a rich vascular flora, including endemic species and genera that are significantly different from the other islands of the Archipelago. These differences are verified through statistical analysis of the existing similarity between the floras of the members of the Canary Islands. This study also analyses the subdivision of Gran Canaria Island, indicating that there are three well-differentiated areas on the island itself. Finally, this study argues that these areas, themselves, should be considered biogeographic sectors.

Effect of habitat fragmentation on levels and patterns of genetic diversity in natural populations of the peat moss Polytrichum commune

Peat bogs represent unique ecosystems that are under particular threat from fragmentation due to peat harvesting, with only 38% of the original peatland in Europe remaining intact and unaffected by peat cutting, drainage and silviculture. In this study, we have used microsatellite markers to determine levels and patterns of genetic diversity in both cut and uncut natural populations of the peat moss Polytrichum commune. Overall diversity levels suggest that there is more genetic variation present than had previously been assumed for bryophytes. Despite this, diversity values from completely cut bogs were found to be lower than those from uncut peatlands (average 0.729 versus 0.880). In addition, the genetic diversity was more highly structured in the cut populations, further suggesting that genetic drift is already affecting genetic diversity in peat bogs subjected to fragmentation.