OnLine Ozonolysis Methods for the Determination of Double Bond Position in Unsaturated Lipids

Modern lipidomics relies heavily on mass spectrometry for the structural characterization and quantification of lipids of biological origins. Structural information is gained by tandem mass spectrometry (MS/MS) whereby lipid ions are fragmented to elucidate lipid class, fatty acid chain length, and degree of unsaturation. Unfortunately, however, in most cases double bond position cannot be assigned based on MS/MS data alone and thus significant structural diversity is hidden from such analyses. For this reason, we have developed two online methods for determining double bond position within unsaturated lipids; ozone electrospray ionization mass spectrometry (OzESI-MS) and ozone-induced dissociation (OzID). Both techniques utilize ozone to cleave C-C double bonds that result in chemically induced fragment ions that locate the position(s) of unsaturation

Surface analysis of lipids by mass spectrometry : More than just imaging

Mass spectrometry is now an indispensable tool for lipid analysis and is arguably the driving force in the renaissance of lipid research. In its various forms, mass spectrometry is uniquely capable of resolving the extensive compositional and structural diversity of lipids in biological systems. Furthermore, it provides the ability to accurately quantify molecular-level changes in lipid populations associated with changes in metabolism and environment; bringing lipid science to the "omics" age. The recent explosion of mass spectrometry-based surface analysis techniques is fuelling further expansion of the lipidomics field. This is evidenced by the numerous papers published on the subject of mass spectrometric imaging of lipids in recent years. While imaging mass spectrometry provides new and exciting possibilities, it is but one of the many opportunities direct surface analysis offers the lipid researcher. In this review we describe the current state-of-the-art in the direct surface analysis of lipids with a focus on tissue sections, intact cells and thin-layer chromatography substrates. The suitability of these different approaches towards analysis of the major lipid classes along with their current and potential applications in the field of lipid analysis are evaluated. © 2013 Elsevier Ltd. All rights reserved.

Whole-genome sequencing reveals untapped genetic potential in Africa’s indigenous cereal crop sorghum

Sorghum is a food and feed cereal crop adapted to heat and drought and a staple for 500 million of the world’s poorest people. Its small diploid genome and phenotypic diversity make it an ideal C4 grass model as a complement to C3 rice. Here we present high coverage (16–45 × ) resequenced genomes of 44 sorghum lines representing the primary gene pool and spanning dimensions of geographic origin, end-use and taxonomic group. We also report the first resequenced genome of S. propinquum, identifying 8 M high-quality SNPs, 1.9 M indels and specific gene loss and gain events in S. bicolor. We observe strong racial structure and a complex domestication history involving at least two distinct domestication events. These assembled genomes enable the leveraging of existing cereal functional genomics data against the novel diversity available in sorghum, providing an unmatched resource for the genetic improvement of sorghum and other grass species.

Is intent-aware expected reciprocal rank sufficient to evaluate diversity?

In this paper we define two models of users that require diversity in search results; these models are theoretically grounded in the notion of intrinsic and extrinsic diversity. We then examine Intent-Aware Expected Reciprocal Rank (ERR-IA), one of the official measures used to assess diversity in TREC 2011-12, with respect to the proposed user models. By analyzing ranking preferences as expressed by the user models and those estimated by ERR-IA, we investigate whether ERR-IA assesses document rankings according to the requirements of the diversity retrieval task expressed by the two models. Empirical results demonstrate that ERR-IA neglects query-intents coverage by attributing excessive importance to redundant relevant documents. ERR-IA behavior is contrary to the user models that require measures to first assess diversity through the coverage of intents, and then assess the redundancy of relevant intents. Furthermore, diversity should be considered separately from document relevance and the documents positions in the ranking.

Equal access to the opportunities available? Equity and diversity laws and policies in Australia

Australia has been populated for more than 40,000 years with Indigenous Australians joined by European settlers only 230 years ago. The first settlers consisted of convicts from more than 28 countries and members of the British army who arrived in 1788 to establish a British penal colony. Mass migration in the nineteenth century with one and a half million immigrants from Europe, principally from the United Kingdom and Ireland (Haines and Shlomowitz, 1992), established the continent as an Anglo society in the Pacific. In the twentieth century immigrants came from many European countries and in the latter decades from many parts of Asia and the Middle East (Collins, 1991, pp.10-13). In the 21st century Australia has an ethnically and culturally diverse population. The original Indigenous population of Australia accounts for approximately 460,000 or 2.5 per cent of the total population (ABS, 2006a). Estimates are that around 4.5m. persons in the population (close to 20 per cent), were born outside Australia with the majority of these arriving from Europe, principally the United Kingdom, and New Zealand (ABS, 2006b). Like many other countries, Australia has a legacy of discrimination and inequality in employment. Propelled by racist ideologies and the male breadwinner ideology, Indigenous Australians, and non-European immigrants, and women were barred from certain jobs and paid less for their work than any white male counterpart. These conditions were legally sanctioned through the industrial relations system and other laws in the nineteenth and first half of the twentieth century. Since the 1960s a dramatic change has occurred in social policy and national legislation and Australia today has an extensive array of laws which forbid employment discrimination on race, ethnicity, gender and many other characteristics, and other approaches which promote proactive organizational plans and actions to achieve equity in employment. This chapter outlines these developments.

Orientation robust transmit polarization diversity techniques

Polarisation diversity is a technique to improve the quality of mobile communications, but its reliability is suboptimal because it depends on the mobile channel and the antenna orientations at both ends of the mobile link. A method to optimise the reliability is established by minimising the dependency on antenna orientations. While the mobile base station can have fixed antenna orientation, the mobile terminal is typically a handheld device with random orientations. This means orientation invariance needs to be established at the receiver in the downlink, and at the transmitter in the uplink. This research presents separate solutions for both cases, and is based on the transmission of an elliptically polarised signal synthesised from the channel statistics. Complete receiver orientation invariance is achieved in the downlink. Effects of the transmitter orientation are minimised in the uplink.

Productive and inclusive? How documentation concealed racialising practices in a diversity project

This article examines how documentation concealed racialising practices in a diversity project that was seen to be productive and inclusive. Documentation examples are taken from a doctoral study about embedding Indigenous perspectives in early childhood education curricula in two Australian urban childcare centres. In place of reporting examples of ‘good’ early childhood education practice, the study labelled racialising practices in educators’ work. The primary aim was to understand how racialising practices are mobilised in professional practices, including documentation, even when educators’ work is seen to be high quality. Extracts from two communal journals that captured an action research process around embedding practices are examined to show how racism and whiteness were concealed within the documentation. This enables understanding about how documentation can provide evidence to stakeholders that diversity work in mainstream childcare centres is productive and inclusive, despite disparity between what is recorded and what occurs in practice.

Using performance-based evaluation to close the loop between biological and robotic navigation

In this paper we describe the benefits of a performance-based approach to modeling biological systems for use in robotics. Specifically, we describe the RatSLAM system, a computational model of the navigation processes thought to drive navigation in a part of the rodent brain called the hippocampus. Unlike typical computational modeling approaches, which focus on biological fidelity, RatSLAM’s development cycle has been driven primarily by performance evaluation on robots navigating in a wide variety of challenging, real world environments. We briefly describe three seminal results, two in robotics and one in biology. In addition, we present current research on brain-inspired learning algorithms with the aim of enabling a robot to autonomously learn how best to use its sensor suite to navigate, without requiring any specific knowledge of the robot, sensor types or environment characteristics. Our aim is to drive discussion on the merits of practical, performance-focused implementations of biological models in robotics.

Sustainable Urban Water Environment : Climate, Pollution and Adaptation

"This multi-disciplinary book provides practical solutions for safeguarding the sustainability of the urban water environment. Firstly, the importance of the urban water environment is highlighted and the major problems urban water bodies face and strategies to safeguard the water environment are explored. Secondly, the diversity of pollutants entering the water environment through stormwater runoff are discussed and modelling approaches for factoring in climate change and future urban and transport scenarios are proposed. Thirdly, by linking the concepts of sustainable urban ecosystems and sustainable urban and transport development, capabilities of two urban sustainability assessment models are demonstrated."--publisher website

Elucidation of double bond position in unsaturated lipids by ozone electrospray ionization mass spectrometry

The position(s) of carbon-carbon double bonds within lipids can dramatically affect their structure and reactivity and thus has a direct bearing on biological function. Commonly employed mass spectrometric approaches to the characterization of complex lipids, however, fail to localize sites of unsaturation within the molecular structure and thus cannot distinguish naturally occurring regioisomers. In a recent communication \[Thomas, M. C.; Mitchell, T. W.; Blanksby, S. J. J. Am. Chem. Soc. 2006, 128, 58-59], we have presented a new technique for the elucidation of double bond position in glycerophospholipids using ozone-induced fragmentation within the source of a conventional electrospray ionization mass spectrometer. Here we report the on-line analysis, using ozone electrospray mass spectrometry (OzESI-MS), of a broad range of common unsaturated lipids including acidic and neutral glycerophospholipids, sphingomyelins, and triacylglycerols. All lipids analyzed are found to form a pair of chemically induced fragment ions diagnostic of the position of each double bond(s) regardless of the polarity, the number of charges, or the adduction (e.g., \[M - H](-), \[M - 2H](2-), \[M + H](+), \[M + Na](+), \[M + NH4](+)). The ability of OzESI-MS to distinguish lipids that differ only in the position of the double bonds is demonstrated using the glycerophosphocholine standards, GPCho(9Z-18:1/9Z-18:1) and GPCho(6Z-18:1/6Z-18:1). While these regioisomers cannot be differentiated by their conventional tandem mass spectra, the OzESI-MS spectra reveal abundant fragment ions of distinctive mass-to-charge ratio (m/z). The approach is found to be sufficiently robust to be used in conjunction with the m/z 184 precursor ion scans commonly employed for the identification of phosphocholine-containing lipids in shotgun lipidomic analyses. This tandem OzESI-MS approach was used, in conjunction with conventional tandem mass spectral analysis, for the structural characterization of an unknown sphingolipid in a crude lipid extract obtained from a human lens. The OzESI-MS data confirm the presence of two regioisomers, namely, SM(d18:0/15Z-24:1) and SM(d18:0/17Z-24:1), and suggest the possible presence of a third isomer, SM(d18:0/19Z-24:1), in lower abundance. The data presented herein demonstrate that OzESI-MS is a broadly applicable, on-line approach for structure determination and, when used in conjunction with established tandem mass spectrometric methods, can provide near complete structural characterization of a range of important lipid classes. As such, OzESI-MS may provide important new insight into the molecular diversity of naturally occurring lipids.

Ozone-induced dissociation : Elucidation of double bond position within mass-selected lipid ions

Ions formed from lipids during electrospray ionization of crude lipid extracts have been mass-selected within a quadrupole linear ion trap mass spectrometer and allowed to react with ozone vapor. Gas-phase ion-molecule reactions between unsaturated lipid ions and ozone are found to yield two primary product ions for each carbon-carbon double bond within the molecule. The mass-to-charge ratios of these chemically induced fragments are diagnostic of the position of unsaturation within the precursor ion. This novel analytical technique, dubbed ozone-induced dissociation (OzID), can be applied both in series and in parallel with conventional collision-induced dissociation (CID) to provide near-complete structural assignment of unknown lipids within complex mixtures without prior fractionation or derivatization. In this study, OzID is applied to a suite of complex lipid extracts from sources including human lens, bovine kidney, and commercial olive oil, thus demonstrating the technique to be applicable to a broad range of lipid classes including both neutral and acidic glycerophospholipids, sphingomyelins, and triacylglycerols. Gas-phase ozonolysis reactions are also observed with different types of precursor ions including \[M + H](+), \[M + Li](+), \[M + Na](+), and \[M H](-): in each case yielding fragmentation data that allow double bond position to be unambiguously assigned. Within the human lens lipid extract, three sphingomyelin regioisomers, namely SM(d18:0/15Z-24:1), SM(d18:0/17Z-24:1), and SM(d18:0/19Z-24:1), and a novel phosphatidylethanolamine alkyl ether, GPEtn(11Z-18:1e/9Z18:1), are identified using a combination of CID and OzID. These discoveries demonstrate that lipid identification based on CID alone belies the natural structural diversity in lipid biochemistry and illustrate the potential of OzID as a complementary approach within automated, high-throughput lipid analysis protocols.

Exploring sustainability themes in engineering accreditation and curricula

Purpose This paper aims to present key findings from an inquiry into engineering accreditation and curricula renewal. The research attempted to ascertain conceptions of requisite sustainability themes among engineering academics and professionals. The paper also reflects on the potential role of professional engineering institutions (PEIs) in embedding sustainability through their programme accreditation guidelines and wider implications in terms of rapid curricula renewal. Design/methodology/approach This research comprised an International Engineering Academic Workshop held during the 2010 International Symposium on Engineering Education in Ireland, on “accreditation and sustainable engineering”. This built on the findings of a literature review that was distributed prior to the workshop. Data collection included individual questionnaires administered during the workshop, and notes scribed by workshop participants. Findings The literature review highlighted a wide range of perspectives across and within engineering disciplines, regarding what sustainability/sustainable development (SD) themes should be incorporated into engineering curricula, and regarding language and terminology. This was also reflected in the workshop discussions. Notwithstanding this diversity, clusters of sustainability themes and priority considerations were distilled from the literature review and workshop. These related to resources, technology, values, ethics, inter- and intra-generational equity, transdisciplinarity, and systems and complex thinking. Themes related to environmental and economic knowledge and skills received less attention by workshop participants than represented in the literature. Originality/value This paper provides an appreciation of the diversity of opinion regarding priority sustainability themes for engineering curricula, among a group of self-selected engineering academics who have a common interest in education for SD. It also provides some insights and caveats on how these themes might be rapidly integrated into engineering curricula.

A multi-genome analysis approach enables tracking of the invasion of a single Russian wheat aphid (Diuraphis noxia) clone throughout the New World

This study investigated the population genetics, demographic history and pathway of invasion of the Russian wheat aphid (RWA) from its native range in Central Asia, the Middle East and Europe to South Africa and the Americas. We screened microsatellite markers, mitochondrial DNA and endosymbiont genes in 504 RWA clones from nineteen populations worldwide. Following pathway analyses of microsatellite and endosymbiont data, we postulate that Turkey and Syria were the most likely sources of invasion to Kenya and South Africa, respectively. Furthermore, we found that one clone transferred between South Africa and the Americas was most likely responsible for the New World invasion. Finally, endosymbiont DNA was found to be a high resolution population genetic marker, extremely useful for studies of invasion over a relatively short evolutionary history time frame. This study has provided valuable insights into the factors that may have facilitated the recent global invasion by this damaging pest.

A molecular phylogeny of the checkered beetles and a description of Epiclininae a new subfamily (Coleoptera: Cleroidea: Cleridae)

We provide the first molecular phylogeny of the clerid lineage (Coleoptera: Cleridae, Thanerocleridae) within the superfamily Cleroidea to examine the two most recently-proposed hypotheses of higher-level classification. Phylogenetic relationships of checkered beetles were inferred from approximately ~5,000nt of both nuclear and mitochondrial rDNA (28S, 16S, and 12S) and the mitochondrial protein-coding gene COI. A worldwide sample of ~70 genera representing almost a quarter of generic diversity of the clerid lineage was included and phylogenies were reconstructed using Bayesian and Maximum Likelihood approaches. Results support the monophyly of many proposed subfamilies but were not entirely congruent with either current classification system. The subfamilial relationships within the Cleridae are resolved with support for three main lineages. Tillinae are supported as the sister group to all other subfamilies within the Cleridae, whereas Thaneroclerinae, Korynetinae and a new subfamily formally described here, Epiclininae subf. n, form a sister group to Clerinae + Hydnocerinae.

Analysis of the NF-κB p50 dimer interface by diversity screening

An in vivo screen has been devised for NF-κB p50 activity in Escherichia coli exploiting the ability of the mammalian transcription factor to emulate a prokaryotic repressor. Active intracellular p50 was shown to repress the expression of a green fluorescent protein reporter gene allowing for visual screening of colonies expressing active p50 on agar plates. A library of mutants was constructed in which the residues Y267, L269, A308 and V310 of the dimer interface were simultaneously randomised and twenty-five novel functional interfaces were selected which repressed the reporter gene to similar levels as the wild-type protein. The leucine-269 alanine-308 core was repeatedly, but not exclusively, selected from the library whilst a diversity of predominantly non-polar residues were selected at positions 267 and 310. These results indicate that L269 and A308 may form a hot spot of interaction and allow an insight into the processes of dimer selectivity and evolution within this family of transcription factors.