Formation of neutral molecules of potential stellar interest by neutralisation of negative ions in a mass spectrometer - The application of experiment and molecular modelling in concert

This paper is a modified version of a lecture which describes the synthesis, structure and reactivity of some neutral molecules of stellar significance. The neutrals are formed in the collision cell of a mass spectrometer following vertical Franck-Condon one electron oxidation of anions of known bond connectivity. Neutrals are characterised by conversion to positive ions and by extensive theoretical studies at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31G(d) level of theory. Four systems are considered in detail, viz (i) the formation of linear C-4 and its conversion to the rhombus C-4, (ii) linear C-5 and the atom scrambling of this system when energised, (iii) the stable cumulene oxide CCCCCO, and (iv) the elusive species O2C-CO. This paper is not intended to be a review of interstellar chemistry: examples are selected from our own work in this area. (C) 2002 Elsevier Science Inc. All rights reserved.

A mass spectrometry study of XCO+, X = Si, Ge : Is SiCO+ a main group carbonyl? Comments on the bonding in ground state SiCO and the Si,C,O (+) potential energy surface

The cation\[Si,C,O](+) has been generated by 1) the electron ionisation (EI) of tetramethoxysilane and 2) chemical ionisation (CI) of a mixture of silane and carbon monoxide. Collisional activation (CA) experiments performed for mass-selected \[Si,C,O](+), generated by using both methods, indicate that the structure is not inserted OSiC+; however, a definitive structural assignment as Si+-CO, Si+-OC or some cyclic variant is impossible based on these results alone. Neutralisation-reionisation (+NR+) experiments for EI-generated \[Si,C,O](+) reveal a small peak corresponding to SiC+, but no detectable SiO+ signal, and thus establishes the existence of the Si+-CO isomer. CCSD(T)//B3LYP calculations employing a triple-zeta basis set have been used to explore the doublet and quartet potential-energy surfaces of the cation, as well as some important neutral states The results suggest that both Si+-CO and Si+ - OC isomers are feasible; however, the global minimum is (2)Pi SiCO+. Isomeric (2)Pi SiOC+ is 12.1 kcal mol(-1) less stable than (2)Pi SiCO+, and all quartet isomers are much higher in energy. The corresponding neutrals Si-CO and Si-OC are also feasible, but the lowest energy Si - OC isomer ((3)A") is bound by only 1.5 kcal mol(-1). We attribute most, if nor all, of the recovery signal in the +NR' experiment to SiCO+ survivor ions. The nature of the bonding in the lowest energy isomers of Si+ -(CO,OC) is interpreted with the aid of natural bond order analyses, and the ground stale bonding of SiCO+ is discussed in relation to classical analogues such as metal carbonyls and ketenes.

Structural identification of hindered amine light stabilisers in coil coatings using electrospray ionisation tandem mass spectrometry

Hindered amine light stabilisers (HALS) are the most effective antioxidants currently available for polymer systems in post-production, in-service applications, yet the mechanism of their action is still not fully understood. Structural characterisation of HALS in polymer matrices, particularly the identification of structural modifications brought about by oxidative conditions, is critical to aid mechanistic understanding of the prophylactic effects of these molecules. In this work, electrospray ionisation tandem mass spectrometry (ESI-MS/MS) was applied to the analysis of a suite of commercially available 2,2,6,6-tetramethylpiperidine-based HALS. Fragmentation mechanisms for the \[M + H](+) ions are proposed, which provide a rationale for the product ions observed in the MS/MS and MS(3) mass spectra of N-H, N-CH(3), N-C(O)CH(3) and N-OR containing HALS (where R is an alkyl substituent). A common product ion at m/z 123 was identified for the group of antioxidants containing N-H, N-CH3 or N-C(0)CH3 functionality, and this product ion was employed in precursor ion scans on a triple quadrupole mass spectrometer to identify the HALS species present in a crude extract from of a polyester-based coil coating. Using MS/MS, two degradation products were unambiguously identified. This technique provides a simple and selective approach to monitoring HALS structures within complex matrices. Copyright (C) 2010 John Wiley & Sons, Ltd.

Feasibility and efficacy of a church-based intervention to promote physical activity in children

Background This study evaluated the feasibility and preliminary efficacy of a church-based intervention to promote physical activity (PA) in children. Methods The study was conducted in 4 churches located in 2 large metropolitan areas and 2 regional towns in Kansas. Churches in the intervention condition implemented the "Shining Like Stars" physical activity curriculum module during their regularly scheduled Sunday school classes. Churches in the control condition delivered the same content without integrating physical activity into the lessons. In addition to the curriculum, the intervention churches completed a series of weekly family devotional activities designed to promote parental support for PA and increase PA outside of Sunday school. Results Children completing the Shining Like Stars curriculum exhibited significantly greater amounts of MVPA than those in the control condition (20 steps/min vs. 7 steps/min). No intervention effects were observed for PA levels outside of Sunday school or parental support for PA; however, relative to controls, children in the intervention churches did exhibit a significant reduction in screen time. Conclusion The findings confirm that the integration of physical activity into Sunday school is feasible and a potentially effective strategy for promoting PA in young children.

Engendering the responsibility to protect : women and the prevention of mass atrocities

This article explores the relationship between the Responsibility to Protect (R2P) and the pursuit of the so-called ‘Women, Peace and Security’ (WPS) agenda at the UN. We ask whether the two agendas should continue to be pursued separately or whether each can make a useful contribution to the other. We argue that while the history of R2P has not included language that deliberately evokes the protection of women and the promotion of gender in preventing genocide and mass atrocities, this does not preclude the R2P and WPS agendas becoming mutually reinforcing. The article identifies cross-cutting areas where the two agendas may be leveraged for the UN and member states to address the concerns of women as both actors in need of protection and active agents in preventing and responding to genocide and mass atrocities, namely in the areas of early warning.

Knowledge Based Urban Development

The changing and challenging conditions of the 21st century have been significantly impacting our economy, society and built and natural environments. Today generation of knowledge—mostly in the form of technology and innovation—is seen as a panacea for the adaptation to changes and management of challenges (Yigitcanlar, 2010a). Making space and place that concentrate on knowledge generation, thus, has become a priority for many nations (van Winden, 2010). Along with this movement, concepts like knowledge cities and knowledge precincts are coined as places where citizenship undertakes a deliberate and systematic initiative for founding its development on the identification and sustainable balance of its shared value system, and bases its ability to create wealth on its capacity to generate and leverage its knowledge capabilities (Carrillo, 2006; Yigitcanlar, 2008a). In recent years, the term knowledge precinct (Hu & Chang, 2005) in its most contemporary interpretation evolved into knowledge community precinct (KCP). KCP is a mixed-use post-modern urban setting—e.g., flexible, decontextualized, enclaved, fragmented—including a critical mass of knowledge enterprises and advanced networked infrastructures, developed with the aim of collecting the benefits of blurring the boundaries of living, shopping, recreation and working facilities of knowledge workers and their families. KCPs are the critical building blocks of knowledge cities, and thus, building successful KCPs significantly contributes to the formation of prosperous knowledge cities. In the literature this type of development—a place containing economic prosperity, environmental sustainability, just socio‐spatial order and good governance—is referred as knowledge-based urban development (KBUD). This chapter aims to provide a conceptual understanding on KBUD and its contribution to the building of KCPs that supports the formation of prosperous knowledge cities.

Analysis of albumin-associated peptides and proteins from ovarian cancer patients

Albumin binds low–molecular-weight molecules, including proteins and peptides, which then acquire its longer half-life, thereby protecting the bound species from kidney clearance. We developed an experimental method to isolate albumin in its native state and to then identify [mass spectrometry (MS) sequencing] the corresponding bound low–molecular-weight molecules. We used this method to analyze pooled sera from a human disease study set (high-risk persons without cancer, n= 40; stage I ovarian cancer, n = 30; stage III ovarian cancer, n = 40) to demonstrate the feasibility of this approach as a discovery method. Methods Albumin was isolated by solid-phase affinity capture under native binding and washing conditions. Captured albumin-associated proteins and peptides were separated by gel electrophoresis and subjected to iterative MS sequencing by microcapillary reversed-phase tandem MS. Selected albumin-bound protein fragments were confirmed in human sera by Western blotting and immunocompetition. Results In total, 1208 individual protein sequences were predicted from all 3 pools. The predicted sequences were largely fragments derived from proteins with diverse biological functions. More than one third of these fragments were identified by multiple peptide sequences, and more than one half of the identified species were in vivo cleavage products of parent proteins. An estimated 700 serum peptides or proteins were predicted that had not been reported in previous serum databases. Several proteolytic fragments of larger molecules that may be cancer-related were confirmed immunologically in blood by Western blotting and peptide immunocompetition. BRCA2, a 390-kDa low-abundance nuclear protein linked to cancer susceptibility, was represented in sera as a series of specific fragments bound to albumin. Conclusion Carrier-protein harvesting provides a rich source of candidate peptides and proteins with potential diverse tissue and cellular origins that may reflect important disease-related information.

Third harmonic generation of the surface wave in the semiconductor-metal slowing-down structure

A nonlinear process is considered of the surface wave third harmonics generation in a slowing-down semiconductor-metal structure. The process is conditioned by non-parabolicity of the charge carrier dispersion law. It is shown that in narrow-gap semiconducting materials it is necessary to account for the process together with the surface wave second harmonics generation conditioned by nonlinearity of quasi-hydrodynamics and the Maxwell equations. The conclusion is made that the third harmonies amplitude in narrow-gap semiconductors may exceed substantially the signal amplitude at the 3w frequency in a gas plasma and be of the same order with the surface waves second harmonies amplitude.

The importance of science fiction and other STEM-related mass media in young people’s decisions to enrol in university STEM courses

This paper presents Australian results from the Interests and Recruitment in Science (IRIS) study with respect to the influence of STEM-related mass media, including science fiction, on students’ decisions to enrol in university STEM courses. The study found that across the full cohort (N=2999), students tended to attribute far greater influence to science-related documentaries/channels such as Life on Earth and the Discovery Channel, etc. than to science-fiction movies or STEM-related TV dramas. Males were more inclined than females to consider science fiction/fantasy books and films and popular science books/magazines as having been important in their decisions. Students taking physics/astronomy tended to rate the importance of science fiction/fantasy books and films higher than students in other courses. The implications of these results for our understanding of influences on STEM enrolments are discussed.

Determinants and measurement of lean body mass in Indian adults

Indians tend to have lower lean body mass than other ethnic groups which increases the risk of chronic diseases. Three complementary studies included in this thesis advanced knowledge on determinants of lean body mass in Indians and the techniques to measure it. The first study examined the determinants of lean body mass in young Indian adults and highlighted the importance of diet and physical activity for development of lean body mass. This study has important implications for policy on prevention of chronic diseases in India. The other two studies helped refinement of the techniques of lean body mass measurement and are expected to facilitate future research in this area. The thesis is presented in the form of publications in high ranking journals.

Gambling & gaming : power relations in dispute resolution

Who, ultimately, has power? Is it the senior executive with his finger on the off switch, is it the users themselves who make the decision to participate and contribute financially, or is it those who report on the actions of the company with the ability to reach large numbers of existing and potential players? In both the gambling and gaming industries, power is up for grabs. This work undertakes to consider how norms are formed in online gaming communities; that is, how the developers and players negotiate amongst themselves both how the game will operate. Also considered is how to resolve disputes that arise, and what power and limitations each side has when they need to make an impact – from developers switching off the server, to players quitting en-mass or causing disruption within the environment (using the recent example of Eve Online). Outside of the direct sphere of the game however a third party lurks – commentators. These may take the form of well established review sites, community forums or, in the case of the gambling industry, dispute resolution services but their power stake is clear – by publicising and interpreting the acts of both developers and players, they are in a position to influence whether current players stick with a company, whether new players join a company and how the company is perceived in the wider community.

Proceedings of the Third International Workshop on Theory and Applications of Process Visualization

This is the third TAProViz workshop being run at BPM. The intention this year is to consolidate on the results of the previous successful workshops by further developing this important topic, identifying the key research topics of interest to the BPM visualization community. We note this year the continuing interest in the visualisation of process mining data and resultant process models. More info at: http://wst.univie.ac.at/topics/taproviz14/

Lessons from a Church Mural

A travel article about the Moselle Valley, Germany. There’s a school of thought that says you shouldn’t look back in life. This is not the received wisdom in Cochem, a village on the Moselle river known, like many others in the area, for its white wine and fairytale castle. Here, they say, it’s bad luck if you don’t turn around for one last look at a mural of St Christopher that graces the castle’s main tower...