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.

Trust, leadership and economic necessity in post-compulsory education

Trust is a complex concept that has increasingly been debated in academic research (Kramer and Tyler, 1996). Research on 'trust and leadership' (Caldwell and Hayes, 2007) has suggested, unsurprisingly, that leadership behaviours influence 'follower' perceptions of leaders' trustworthiness. The development of 'ethical stewardship' amongst leaders may foster high trust situations (Caldwell, Hayes, Karri and Bernal, 2008), yet studies on the erosion of teacher professionalism in UK post-compulsory education have highlighted the distrust that arguably accompanies 'new managerialism', performativity and surveillance within a climate of economic rationalisation established by recent deterministic skills-focused government agendas for education (Avis, 2003; Codd, 1999, Deem, 2004, DFES, 2006). Given the shift from community to commercialism identified by Collinson and Collinson (2005) in a global economic environment characterised by uncertainty and rapid change, trust is, simultaneously, increasingly important and progressively both more fragile and limited in a post compulsory education sector dominated by skills-based targets and inspection demands. Building on such prior studies, this conference paper reports on the analysis of findings from a 2007-8 funded research study on 'trust and leadership' carried out in post-compulsory education. The research project collected and analysed case study interview and survey data from the lifelong learning sector, including selected tertiary, further and higher education (FE and HE) institutions. We interviewed 18 UK respondents from HE and FE, including principals, middle managers, first line managers, lecturers and researchers, supplementing and cross-checking this with a small number of survey responses (11) on 'trust and leadership' and a larger number (241) of survey responses on more generalised leadership issues in post-compulsory education. A range of facilitators and enablers of trust and their relationship to leadership were identified and investigated. The research analysed the ways in which interviewees defined the concept of 'trust' and the extent to which they identified that trust was a mediating factor affecting leadership and organisational performance. Prior literature indicates that trust involves a psychological state in which, despite dependency, risk and vulnerability, trustors have some degree of confident expectation that trustees will behave in benevolent rather than detrimental ways. The project confirmed the views of prior researchers (Mayer, Davis and Schoorman, 1995) that, since trust inevitably involves potential betrayal, estimations of leadership 'trustworthiness' are based on followers' cognitive and affective perceptions of the reliability, competence, benevolence and reputation of leaders. During the course of the interviews it also became clear that some interviewees were being managed in more or less transaction-focused, performative, audit-dominated cultures in which trust was not regarded as particularly important: while 'cautious trust' existed, collegiality flourished only marginally in small teams. Economic necessity and survival were key factors influencing leadership and employee behaviours, while an increasing distance was reported between senior managers and their staff. The paper reflects on the nature of the public sector leadership and management environment in post-compulsory education reported by interviewees and survey respondents. Leadership behaviours to build trust are recommended, including effective communication, honesty, integrity, authenticity, reliability and openness. It was generally felt that building trust was difficult in an educational environment largely determined by economic necessity and performativity. Yet, despite this, the researchers did identify a number of examples of high trust leadership situations that are worthy of emulation.

Trust and Leadership in Higher Education in the Downturn

This Leadership Academy Workshop presentation focused on 'Trust and Leadership in the Downturn', with particular reference to the public sector and to education. The presentation discussed a range of definitions of trust, including the view of Mayer, Davis and Schoorman (1995) that trust can be described as 'the willingness of a person to be vulnerable to the actions of another, based on the expectation that the other will perform a particular action important to the trustor, irrespective of the ability to monitor or control that action'. The presentation then focused on the reasons why this relational psychological state is important,particularly in an economic recession when people were facing job cuts and economic uncertainty in a wider political and social environment characterised by cynicism and a downturn in trust. If trust is defined in part as a belief in the honesty, competence and benevolence of others, it tends to act like 'social glue', cushioning difficult situations and enabling actions to take place easily that otherwise would not be permissible. A worrying state of affairs has recently been developing across the world, however, in the economic downturn, as reported in the Edelman Trust Barometer for 2009, in which there was a marked diminuition of trust in corporations, businesses and government, as a result of the credit crunch. While the US and parts of Europe was showing recovery from a generalised loss of trust by mid-year 2009, the UK had not. It seems that social attitudes in Britain may be hardening - it seems that from being a nation of sceptics we may be becoming a nation of cynics: for example, 69% of the population surveyed by Edelman trust the government less than six months ago. In this situation, there is a need to promote positive measures to build trust, including the establishment of more transparent and honest business practices and practices to ensure that employees are treated well. Following the presentation, a workshop was held to discuss the nature of a possible loss of trust in the downturn in the UK and its implications for leadership practices and development.