Ambient ionisation mass spectrometry for the characterisation of polymers and polymer additives : A review

The purpose of this review is to showcase the present capabilities of ambient sampling and ionisation technologies for the analysis of polymers and polymer additives by mass spectrometry (MS) while simultaneously highlighting their advantages and limitations in a critical fashion. To qualify as an ambient ionisation technique, the method must be able to probe the surface of solid or liquid samples while operating in an open environment, allowing a variety of sample sizes, shapes, and substrate materials to be analysed. The main sections of this review will be guided by the underlying principle governing the desorption/extraction step of the analysis; liquid extraction, laser ablation, or thermal desorption, and the major component investigated, either the polymer itself or exogenous compounds (additives and contaminants) present within or on the polymer substrate. The review will conclude by summarising some of the challenges these technologies still face and possible directions that would further enhance the utility of ambient ionisation mass spectrometry as a tool for polymer analysis. (C) 2013 Elsevier B. V. All rights reserved.

Characterising in situ activation and degradation of hindered amine light stabilisers using liquid extraction surface analysis-mass spectrometry

Changes in the molecular structure of polymer antioxidants such as hindered amine light stabilisers (HALS) is central to their efficacy in retarding polymer degradation and therefore requires careful monitoring during their in-service lifetime. The HALS, bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (TIN123) and bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (TIN292), were formulated in different polymer systems and then exposed to various curing and ageing treatments to simulate in-service use. Samples of these coatings were then analysed directly using liquid extraction surface analysis (LESA) coupled with a triple quadrupole mass spectrometer. Analysis of TIN123 formulated in a cross-linked polyester revealed that the polymer matrix protected TIN123 from undergoing extensive thermal degradation that would normally occur at 292 degrees C, specifically, changes at the 1- and 4-positions of the piperidine groups. The effect of thermal versus photo-oxidative degradation was also compared for TIN292 formulated in polyacrylate films by monitoring the in situ conversion of N-CH3 substituted piperidines to N-H. The analysis confirmed that UV light was required for the conversion of N-CH3 moieties to N-H - a major pathway in the antioxidant protection of polymers - whereas this conversion was not observed with thermal degradation. The use of tandem mass spectrometric techniques, including precursor-ion scanning, is shown to be highly sensitive and specific for detecting molecular-level changes in HALS compounds and, when coupled with LESA, able to monitor these changes in situ with speed and reproducibility. (C) 2013 Elsevier B. V. All rights reserved.

Desorption electrospray ionisation mass spectrometry of stabilised polyesters reveals activation of hindered amine light stabilisers

The use of hindered amine light stabilizers (HALS) to retard thermo- and photo-degradation of polymers has become increasingly common. Proposed mechanisms of polymer stabilisation involve significant changes to the HALS chemical structure; however, reports of the characterisation of these modified chemical species are limited. To better understand the fate of HALS and determine their in situ modifications, desorption electrospray ionisation mass spectrometry (DESI-MS) was employed to characterise ten commercially available HALS present in polyester-based coil coatings. TINUVIN® 770, 292, 144, 123, 152, and NOR371; HOSTAVIN® 3052, 3055, 3050, and 3058 were separately formulated with a pigmented, thermosetting polyester resin, cured on metal at 262 C and analysed directly by DESI-MS. High-level ab initio molecular orbital theory calculations were also undertaken to aid the mechanistic interpretation of the results. For HALS containing N-substituted piperidines (i.e., N-CH3, N-C(O)CH3, and N-OR) a secondary piperidine (N-H) analogue was detected in all cases. The formation of these intermediates can be explained either through hydrogen abstraction based mechanisms or direct N-OR homolysis with the former dominant under normal service temperatures (ca. 25-80 C), and the latter potentially becoming competitive under the high temperatures associated with curing (ca. 230-260 C). © 2013 Elsevier Ltd. All rights reserved.

Structural characterization of glycerophospholipids by combinations of ozone- and collision-induced dissociation mass spectrometry: The next step towards "top-down" lipidomics

The complete structural elucidation of complex lipids, including glycerophospholipids, using only mass spectrometry represents a major challenge to contemporary analytical technologies. Here, we demonstrate that product ions arising from the collision-induced dissociation (CID) of the [M + Na] + adduct ions of phospholipids can be isolated and subjected to subsequent gas-phase ozonolysis-known as ozone-induced dissociation (OzID)-in a linear ion-trap mass spectrometer. The resulting CID/OzID experiment yields abundant product ions that are characteristic of the acyl substitution on the glycerol backbone (i.e., sn-position). This approach is shown to differentiate sn-positional isomers, such as the regioisomeric phosphatidylcholine pair of PC 16:0/18:1 and PC 18:1/16:0. Importantly, CID/OzID provides a sensitive diagnostic for the existence of an isomeric mixture in a given sample. This is of very high value for the analysis of tissue extracts since CID/OzID analyses can reveal changes in the relative abundance of isomeric constituents even within different tissues from the same animal. Finally, we demonstrate the ability to assign carbon-carbon double bond positions to individual acyl chains at specific backbone positions by adding subsequent CID and/or OzID steps to the workflow and that this can be achieved in a single step using a hybrid triple quadrupole-linear ion trap mass spectrometer. This unique approach represents the most complete and specific structural analysis of lipids by mass spectrometry demonstrated to date and is a significant step towards comprehensive top-down lipidomics. This journal is © The Royal Society of Chemistry 2014. Grant Number ARC/DP0986628, ARC/FT110100249, ARC/LP110200648

Rapid differentiation of isomeric lipids by photodissociation mass spectrometry of fatty acid derivatives

RATIONALE Both traditional electron ionization and electrospray ionization tandem mass spectrometry have demonstrated limitations in the unambiguous identification of fatty acids. In the former case, high electron energies lead to extensive dissociation of the radical cations from which little specific structural information can be obtained. In the latter, conventional collision-induced dissociation (CID) of even-electron ions provides little intra-chain fragmentation and thus few structural diagnostics. New approaches that harness the desirable features of both methods, namely radical-driven dissociation with discrete energy deposition, are thus required. METHODS Herein we describe the derivatization of a structurally diverse suite of fatty acids as 4-iodobenzyl esters (FAIBE). Electrospray ionization of these derivatives in the presence of sodium acetate yields abundant [M+Na]+ ions that can be mass-selected and subjected to laser irradiation (=266nm) on a modified linear ion-trap mass spectrometer. RESULTS Photodissociation (PD) of the FAIBE derivatives yields abundant radical cations by loss of atomic iodine and in several cases selective dissociation of activated carboncarbon bonds (e.g., at allylic positions) are also observed. Subsequent CID of the [M+NaI]center dot+ radical cations yields radical-directed dissociation (RDD) mass spectra that reveal extensive carboncarbon bond dissociation without scrambling of molecular information. CONCLUSIONS Both PD and RDD spectra obtained from derivatized fatty acids provide a wealth of structural information including the position(s) of unsaturation, chain-branching and hydroxylation. The structural information obtained by this approach, in particular the ability to rapidly differentiate isomeric lipids, represents a useful addition to the lipidomics tool box. Copyright (c) 2013 John Wiley & Sons, Ltd.

Rapid quantification of free cholesterol in tears using direct insertion/electron ionization-Mass spectrometry

Purpose. To establish a simple and rapid analytical method, based on direct insertion/electron ionization-mass spectrometry (DI/EI-MS), for measuring free cholesterol in tears from humans and rabbits. Methods. A stable-isotope dilution protocol employing DI/EI-MS in selected ion monitoring mode was developed and validated. It was used to quantify the free cholesterol content in human and rabbit tear extracts. Tears were collected from adult humans (n = 15) and rabbits (n = 10) and lipids extracted. Results. Screening, full-scan (m/z 40-600) DI/EI-MS analysis of crude tear extracts showed that diagnostic ions located in the mass range m/z 350 to 400 were those derived from free cholesterol, with no contribution from cholesterol esters. DI/EI-MS data acquired using selected ion monitoring (SIM) were analyzed for the abundance ratios of diagnostic ions with their stable isotope-labeled analogues arising from the D6-cholesterol internal standard. Standard curves of good linearity were produced and an on-probe limit of detection of 3 ng (at 3:1 signal to noise) and limit of quantification of 8 ng (at 10:1 signal to noise). The concentration of free cholesterol in human tears was 15 ± 6 μg/g, which was higher than in rabbit tears (10 ± 5 μg/g). Conclusions. A stable-isotope dilution DI/EI-SIM method for free cholesterol quantification without prior chromatographic separation was established. Using this method demonstrated that humans have higher free cholesterol levels in their tears than rabbits. This is in agreement with previous reports. This paper provides a rapid and reliable method to measure free cholesterol in small-volume clinical samples. © 2013 The Association for Research in Vision and Ophthalmology, Inc.

New media [Fourth Edition]

This is the fourth edition of New Media: An Introduction, with the previous editions being published by Oxford University Press in 2002, 2005 and 2008. As the first edition of the book published in the 2010s, every chapter has been comprehensively revised, and there are new chapters on: • Online News and the Future of Journalism (Chapter 7) • New Media and the Transformation of Higher Education (Chapter 10) • Online Activism and Networked Politics (Chapter 12). It has retained popular features of the third edition, including the twenty key concepts in new media (Chapter 2) and illustrative case studies to assist with teaching new media. The case studies in the book cover: the global internet; Wikipedia; transmedia storytelling; Media Studies 2.0; the games industry and exploitation; video games and violence; WikiLeaks; the innovator’s dilemma; massive open online courses (MOOCs); Creative Commons; the Barack Obama Presidential campaigns; and the Arab Spring. Several major changes in the media environment since the publication of the third edition stand out. Of particular importance has been the rise of social media platforms such as Facebook, Twitter and YouTube, which draw out even more strongly the features of the internet as networked and participatory media, with a range of implications across the economy, society and culture. In addition, the political implications of new media have become more apparent with a range of social media-based political campaigns, from Barack Obama’s successful Presidential election campaigns to the Occupy movements and the Arab Spring. At the same time, the subsequent developments of politics in these and other cases has drawn attention to the limitations of thinking about the politics or the public sphere in technologically determinist ways. When the first edition of New Media was published in 2002, the concept of new media was seen as being largely about the internet as it was accessed from personal computers. The subsequent decade has seen a proliferation of platforms and devices: we now access media in all forms from our phones and other mobile platforms, therefore we seen television and the internet increasingly converging, and we see a growing uncoupling of digital media content and delivery platforms. While this has a range of implications for media law and policy, from convergent media policy to copyright reform, governments and policy-makers are struggling to adapt to such seismic shifts from mass communications media to convergent social media. The internet is no longer primarily a Western-based medium. Two-thirds of the world’s internet users are now outside of Europe and North America; three-quarters of internet users use languages other than English; and three-quarters of the world’s mobile cellular phone subscriptions are in developing nations. It is also apparent that conducting discussions about how to develop new media technologies and discussions about their cultural and creative content can no longer be separated. Discussions of broadband strategies and the knowledge economy need to be increasingly joined with those concerning the creative industries and the creative economy.

Conditions for Successful Reforms : Characteristics of the Organisation and Culture in Chinese Schools in a Global Context

Reforms to the basic education system in China have reflected an increasing awareness of and openness to new ideas from the global education sphere. Many of the concepts involved in the development and implementation of these reforms, including adopting holistic perspectives of student development; decentralising school governance to facilitate local decision-making to address local needs; and, an increased focus on practical, lifelong learning for all involved in schools, have been promoted in research and policies throughout the world. While working within this global context, the system of schooling in China has retained a unique character that is quite different from education in the West. Drawing on an international project on school transformation, this chapter aims to examine how five secondary schools in Chongqing, a municipality in Southwestern China, have harnessed and aligned their resources to provide effective school governance following the curriculum reforms. Furthermore, the chapter will examine the similarities and differences between the organisational structures and cultures of these schools in China and successful schools in Australia, England, Finland, Wales and the United States.

Nutritional influences over the life course on lean body mass of individuals in developing countries

The double burden of childhood undernutrition and adult-onset adiposity in transitioning societies poses a significant public health challenge. The development of suboptimal lean body mass (LBM) could partly explain the link between these two forms of malnutrition. This review examines the evidence on both the role of nutrition in “developmental programming” of LBM and the nutritional influences that affect LBM throughout the life course. Studies from developing countries assessing the relationship of early nutrition with later LBM provide important insights. Overall, the evidence is consistent in suggesting a positive association of early nutritional status (indicated by birth weight and growth during first 2 years) with LBM in later life. Evidence on the impact of maternal nutritional supplementation during pregnancy on later LBM is inconsistent. In addition, the role of nutrients (protein, zinc, calcium, vitamin D) that can affect LBM throughout the life course is described. Promoting optimal intakes of these important nutrients throughout the life course is important for reducing childhood undernutrition as well as for improving the LBM of adults.

Literature review : A culture of trust enhances performance

In this environmental scan of research and policy literature, the authors consider various definitions of trust as they seek to address and inform the hypothesis that ‘a culture of trust enhances performance’ in schools. The discussion draws on the work of the Australian Institute for Teaching and School Leadership in school leadership and research by Caldwell and Harris (2008) to consider ways in which trust is linked to performance in schools and organisations. It explores the concept of trust as a form of capital available to schools, and highlights how successful school leaders work to align trust, strategy and passion in implementing effective change. At the heart of the review is the relationship between trust and school improvement. An adapted model of the elements of a culture of trust developed by Bryk and Schneider in their influential study of trust in school reform in Chicago is used to frame this aspect of the review. The authors identify four essential categories of relationships that enable schools to be described as having a culture of trust. The review concludes with a discussion of the relationship between trust and school governance.

Socioeconomic position and mass media campaigns to prevent chronic disease

This cross-sectional study of a 45 to 60 year old Brisbane population examined socioeconomic differences in campaign reach, understanding of health language, and effectiveness, of a recent mass media health promotion campaign. Lower socioeconomic groups were reached significantly less and understood significantly less of the health language than higher socioeconomic groups thus contributing to the widening of the health inequality gap.

Creative practices in the design studio culture : collaboration and communication

For the purpose of developing collaborative support in design studio environments, we have carried out ethnographic fieldwork in professional and academic product design studios. Our intention was to understand design practices beyond the productivity point of view and take into account the experiential, inspirational and aesthetical aspects of design practices. Using examples from our fieldwork, we develop our results around three broad themes by which design professionals support communication and collaboration: (1) use of artefacts, (2) use of space and (3) designerly practices. We use the results of our fieldwork for drawing implications for designing technologies for the design studio culture.

Competition Hertz : the culture and practice of car audio competitions

The present paper explores extreme car audio systems and the culture and practices that surround car audio competitions. I begin by examining whether, and how, car audio can be thought of as a 'music scene' and in what ways the culture and practice of car audio may fit within post-subcultural discourses. Following this, I offer a description of car audio competitions, revealing some of the practices that define this aspect of car audio scenes. In particular, I concentrate on sound pressure level (SPL) competitions and some of the interesting aspects of the SPL scene. Finally, I briefly examine how the powerful effects (and affects) of bass frequencies are an important part of the attraction of loud car audio systems and how car audio systems contribute to the territorializing of urban spaces.

Building and sustaining a culture to support peer review of teaching

1. Background/context This presentation will report on emerging results from a two phase project funded by the Australian Learning and Teaching Council (ALTC). The project was designed in partnership with five universities and aimed to embed peer review within the local teaching and learning culture by using a distributive leadership framework. 2. The initiative/practice The presentation will highlight research outcomes that bring together both the fundamentals of peer review of teaching with the broader contextual elements of Integration, Leadership and Development. It will be demonstrated that peer review of teaching can be implemented and have advantages for academic staff, teaching evaluation and an organisation if attention is given to strategies that influence the contexts and cultures of teaching. Peer review as a strategy to develop excellence in teaching is considered from a holistic perspective that by necessity encompasses all elements of an educational environment. Results demonstrate achievements that can be obtained through working to foster conditions needed for sustainable leadership and change. The work has implications for policy, research, teaching development and student outcomes and has potential application world-wide. 3. Method(s) of evaluative data collection and analysis The 2 phase project collected focus group and questionnaire data to inform research results that were analysed using a thematic qualitative approach and statistical exploration. 4. Evidence of effectiveness The presentation will demonstrate the effectiveness of distributive leadership and strategic approaches to working for cultural change through the presentation of project findings.

Developing a culture to support peer review of teaching in higher education

This presentation addresses issues related to leadership, academic development and scholarship of teaching and learning, and highlights research funded by the Australian Office of Learning and Teaching (OLT) designed to embed and sustain peer review of teaching within the culture of 5 Australian universities: Queensland University of Technology, University of Technology, Sydney, University of Adelaide, Curtin University, and Charles Darwin University. Peer review of teaching in higher education will be emphasised as a professional process for providing feedback on teaching and learning practice, which if sustained, can become an effective ongoing strategy for academic development (Barnard et al, 2011; Bell, 2005; Bolt and Atkinson, 2010; McGill & Beaty 2001, 1992; Kemmis & McTaggart, 2000). The research affirms that using developmental peer review models (Barnard et al, 2011; D'Andrea, 2002; Hammersley-Fletcher & Orsmond, 2004) can bring about successful implementation, especially when implemented within a distributive leadership framework (Spillane & Healey, 2010). The project’s aims and objectives were to develop leadership capacity and integrate peer review as a cultural practice in higher education. The research design was a two stage inquiry process over 2 years. The project began in July 2011 and encompassed a development and pilot phase followed by a cascade phase with questionnaire and focus group evaluation processes to support ongoing improvement and measures of outcome. Leadership development activities included locally delivered workshops complemented by the identification and support of champions. To optimise long term sustainability, the project was implemented through existing learning and teaching structures and processes within the respective partner universities. Research outcomes highlight the fundamentals of peer review of teaching and the broader contextual elements of integration, leadership and development, expressed as a conceptual model for embedding peer review of teaching within higher education. The research opens a communicative space about introduction of peer review that goes further than simply espousing its worth and introduction. The conceptual model highlights the importance of development of distributive leadership capacity, integration of policies and processes, and understanding the values, beliefs, assumptions and behaviors embedded in an organizational culture. The presentation overviews empirical findings that demonstrate progress to advance peer review requires an ‘across-the-board’ commitment to embed change, and inherently demands a process that co-creates connection across colleagues, discipline groups, and the university sector. Progress toward peer review of teaching as a cultural phenomenon can be achieved and has advantages for academic staff, scholarship, teaching evaluation and an organisation, if attention is given to strategies that influence the contexts and cultures of teaching practice. Peer review as a strategy to develop excellence in teaching is considered from a holistic perspective that by necessity encompasses all elements of an educational environment and has a focus on scholarship of teaching. The work is ongoing and has implication for policy, research, teaching development and student outcomes, and has potential application world-wide.