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.

Can Pickering emulsion formation aid the removal of creosote DNAPL from porous media?

The purpose of this investigation was to examine the proposition that creosote, emplaced in an initially water saturated porous system, can be removed from the system through Pickering emulsion formation. Pickering emulsions are dispersions of two immiscible fluids in which coalescence of the dispersed phase droplets is hindered by the presence of colloidal particles adsorbed at the interface between the two immiscible fluid phases. Particle trapping is strongly favoured when the wetting properties of the particles are intermediate between strong water wetting and strong oil wetting. In this investigation the necessary chemical conditions for the formation of physically stable creosote-in-water emulsions protected against coalescence by bentonite particles were examined. It was established that physically stable emulsions could be formed through the judicious addition of small amounts of sodium chloride and the surfactant cetyl-trimethylammonium bromide. The stability of the emulsions was initially established by visual inspection. However, experimental determinations of emulsion stability were also undertaken by use of oscillatory rheology. Measurements of the elastic and viscous responses to shear indicated that physically stable emulsions were obtained when the viscoelastic systems showed a predominantly elastic response to shearing. Once the conditions were established for the formation of physically stable emulsions a "proof-of-concept" chromatographic experiment was carried out which showed that creosote could be successfully removed from a saturated model porous system. (C) 2007 Elsevier Ltd. All rights reserved.

South East London Palliative and End of Life Care Education and Training Strategy: Meeting the Education and Training Needs of the Health & Social Care Workforce Involved in the Care of Patients and Carers at the End of Life.

EXECUTIVE SUMMARY Aims 1. The aims of this strategy are • to ensure that a full range of education and training related to the adult end of life care pathway is available across South East London to meet the needs of our health and social care workforce • to enable those responsible for end of life care education and training commissioning to procure comprehensively from a full range of education providers in a systematic and strategic manner. Background 2. The work that underpins this strategy was begun by the South East London Cancer Network via its Palliative and End of Life Care Coordinating Group and then developed by way of the Marie Curie Delivering Choice Programme’s Education and Training work stream.

The role of joint training in practitioner development for learning disability services

The presentation explores and evaluates an innovation in education and training in which two different professional trainings (nursing and social work) are integrated to produce jointly qualified specialist practitioners.

Learners' emotional and psychic responses to encounters with learning support in further education and training

This article investigates the experience of individual learners who have been allocated learning support in the further education system in England. The particular focus is on interviewees' constructions of their emotional and psychic experiences. Through the adoption of a psycho-social perspective, learners' tendency to 'idealise' their learning support workers is understood as a strategy for coping with the anxiety generated by a range of previous experiences. The implications for policy-makers are discussed.

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.

Effects of training peer tutors in content knowledge versus tutoring skills on giving feedback to help tutees’ complex tasks

This study aims to investigate the effectiveness of training tutors in content knowledge of a particular domain versus training them in tutoring skills of pedagogical knowledge when tutoring on a complex tutee task. Forty-seven tutor-tutee pairs of fourth year secondary school students were created and assigned to one of two treatments. Twenty-two tutors received training in content knowledge and the other twenty-five tutors in tutoring skills. Tutors formulated written feedback immediately after the training. Tutees first interpreted the tutor feedback and then used it to revise their research questions. The results showed that tutors trained in tutoring skills formulated more effective feedback than tutors trained in content knowledge. In addition, tutees helped by tutoring-skills tutors found the feedback more motivating than those helped by content- knowledge tutors. However, no differences were found in tutee performance on revision. The findings are discussed in terms of the set-up of this study and implications for improving the effectiveness of peer tutoring.

Simple shade plots aid better long-term choices of data pre-treatment in multivariate assemblage studies

Shade plots, simple visual representations of abundance matrices from multivariate species assemblage studies, are shown to be an effective aid in choosing an overall transformation (or other pre-treatment) of quantitative data for long-term use, striking an appropriate balance between dominant and less abundant taxa in ensuing resemblance-based multivariate analyses. Though the exposition is entirely general and applicable to all community studies, detailed illustrations of the comparative power and interpretative possibilities of shade plots are given in the case of two estuarine assemblage studies in south-western Australia: (a) macrobenthos in the upper Swan Estuary over a two-year period covering a highly significant precipitation event for the Perth area; and (b) a wide-scale spatial study of the nearshore fish fauna from five divergent estuaries. The utility of transformations of intermediate severity is again demonstrated and, with greater novelty, the potential importance seen of further mild transformation of all data after differential down-weighting (dispersion weighting) of spatially clumped' or schooled' species. Among the new techniques utilized is a two-way form of the RELATE test, which demonstrates linking of assemblage structure (fish) to continuous environmental variables (water quality), having removed a categorical factor (estuary differences). Re-orderings of sample and species axes in the associated shade plots are seen to provide transparent explanations at the species level for such continuous multivariate patterns.

Small Proline Rich Protein-2 Expression and Regulation in the Caco-2 model of Intestinal Epithelial Differentiation along the Crypt-Villus Axis

Small proline-rich protein-2 (SPRR2) functions as a determinant of flexibility and permeability in the mature cornified envelope of the skin. SPRR2 is strongly upregulated by the commensal flora and may mediate signaling to differentiated epithelia of the small intestine and colon. Yet, SPRR2 function in the GI tract is largely unexplored. Using the Caco-2 model of intestinal epithelial differentiation along the crypt-villus axis, we hypothesized that SPRR2 would be preferentially expressed in post-confluent differentiated Caco-2 cells and examined SPRR2 regulation by the protein kinase A pathway (PKA) and short chain fatty acids (SCFAs). Differentiation-dependent SPRR2 expression was examined in cytoskeletal-, membrane-, and nuclear-enriched fractions by immunoblotting and confocal immunofluorescence. We studied the effect of SCFAs, known inducers of differentiation, on SPRR2 expression in pre-confluent undifferentiated Caco-2 cells and explored potential mechanisms involved in this induction using MAP kinase inhibitors. SPRR2 expression was also compared between HIEC crypt cells and 16 to 20 week primary fetal villus cells as well as in different segments in mouse small intestine and colon. We determined if SPRR2 is increased by gram negative bacteria such as S. typhimurium. SPRR2 expression increased in a differentiation-dependent manner in Caco-2 cells and was present in human fetal epithelial villus cells but absent in HIEC crypt cells. Differentiation-induced SPRR2 was down-regulated by 8-Br-cAMP as well as by forskolin/IBMX co-treatment. SPRR2 was predominantly cytoplasmic and did not accumulate in Triton X-100-insoluble cytoskeletal fractions. SPRR2 was present in the membrane- and nuclear-enriched fractions and demonstrated co-localization with F-actin at the apical actin ring. No induction was seen with the specific HDAC inhibitor trichostatin A, while SCFAs and the HDAC inhibitor SBHA all induced SPRR2. SCFA responses were inhibited by MAP kinase inhibitors SB203580 and U0126, thus suggesting that the SCFA effect may be mediated by orphan G-protein receptors GPR41 and GPR43. S. typhimurium induced SPRR2 in undifferentiated cells. We conclude that SPRR2 protein expression is associated with differentiated epithelia and is regulated by PKA signaling and by by-products of the bowel flora. This is the first report to establish an in vitro model to study the physiology and regulation of SPRR2.

La existencia de necesidades de información y comportamiento informativo en los entrenadores en deportes de combate

Este trabajo tiene como propósito esencial, realizar un acercamiento para detectar e identificar las necesidades de información y el comportamiento informativo de entrenadores en deportes de combate. Para ello se aplicó un cuestionario a instructores de aikido, boxeo, esgrima, judo, karate, kendo, lima lama, lucha y taekwondo seleccionados mediante un muestreo no probabilístico por causalidad. En general encontramos que los principales temas de interés entre los instructores son: los programas de entrenamiento, nutrición y dietas de entrenamiento. Por otra parte, los entrenadores son más propensos a utilizar su experiencia, internet y cursos para obtener información. En contraste se nota que la biblioteca y los libros son poco usados.