Vibrational spectra of α-amino acids in the zwitterionic state in aqueous solution and the solid state: DFT calculations and the influence of hydrogen bonding

The zwitterionic forms of the two simplest alpha-amino acids, glycine and l-alanine, in aqueous solution and the solid state have been modeled by DFT calculations. Calculations of the structures in the solid state, using PW91 or PBE functionals, are in good agreement with the reported crystal structures, and the vibrational spectra computed at the optimized geometries provide a good fit to the observed IR and Raman spectra in the solid state. DFT calculations of the structures and vibrational spectra of the zwitterions in aqueous solution at the B3-LYP/cc-pVDZ level were found to require both explicit and implicit solvation models. Explicit solvation was modeled by inclusion of five hydrogen-bonded water molecules attached to each of the five possible hydrogen-bonding sites in the zwitterion and the integration equation formalism polarizable continuum model (IEF-PCM) was employed, providing a satisfactory fit to observed IR and Raman spectra. Band assignments are reported in terms of potential-energy distributions, which differ in some respects to those previously reported for glycine and l-alanine.

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.

Theories of the state

[Introduction] The recent, unparalleled ascendancy of the liberal democratic state may seem to render alternative theories of the state redundant. But while the prevailing view might be that “I have seen the future, and it works”, it was not so long ago that this was said about a very different type of state. And while the liberal democratic state is an abundant form of government, in practice this often reflects an uneasy compromise of conflicting conceptions of politics. It thus remains important to unpick the theoretical underpinnings of conceptions of the state.