Energy dependence of methyl-radical adsorption on diamond (001)-(2×1) surface

The deposition of hyperthermal CH3 on diamond (001)-(2×1) surface at room temperature has been studied by means of molecular dynamics simulation using the many-body hydrocarbon potential. The energy threshold effect has been observed. That is, with fixed collision geometry, chemisorption can occur only when the incident energy of CH3 is above a critical value (Eth). Increasing the incident energy, dissociation of hydrogen atoms from the incident molecule was observed. The chemisorption probability of CH3 as a function of its incident energy was calculated and compared with that of C2H2. We found that below 10 eV, the chemisorption probability of C2H2 is much lower than that of CH3 on the same surface. The interesting thing is that it is even lower than that of CH3 on a hydrogen covered surface at the same impact energy. It indicates that the reactive CH3 molecule is the more important species than C2H2 in diamond synthesis at low energy, which is in good agreement with the experimental observation.

Outcomes of the Chemistry Discipline Network Mapping Exercises: Are the Threshold Learning Outcomes met?

The Chemistry Discipline Network has recently completed two distinct mapping exercises. The first is a snapshot of chemistry taught at 12 institutions around Australia in 2011. There were many similarities but also important differences in the content taught and assessed at different institutions. There were also significant differences in delivery, particularly laboratory contact hours, as well as forms and weightings of assessment. The second mapping exercise mapped the chemistry degrees at three institutions to the Threshold Learning Outcomes for chemistry. Importantly, some of the TLOs were addressed by multiple units at all institutions, while others were not met, or were met at an introductory level only. The exercise also exposed some challenges in using the TLOs as currently written.

Acquiring search expertise : learning experiences and threshold concepts

Expert searchers engage with information as information brokers, researchers, reference librarians, information architects, faculty who teach advanced search, and in a variety of other information-intensive professions. Their experiences are characterized by a profound understanding of information concepts and skills and they have an agile ability to apply this knowledge to interacting with and having an impact on the information environment. This study explored the learning experiences of searchers to understand the acquisition of search expertise. The research question was: What can be learned about becoming an expert searcher from the learning experiences of proficient novice searchers and highly experienced searchers? The key objectives were: (1) to explore the existence of threshold concepts in search expertise; (2) to improve our understanding of how search expertise is acquired and how novice searchers, intent on becoming experts, can learn to search in more expertlike ways. The participant sample drew from two population groups: (1) highly experienced searchers with a minimum of 20 years of relevant professional experience, including LIS faculty who teach advanced search, information brokers, and search engine developers (11 subjects); and (2) MLIS students who had completed coursework in information retrieval and online searching and demonstrated exceptional ability (9 subjects). Using these two groups allowed a nuanced understanding of the experience of learning to search in expertlike ways, with data from those who search at a very high level as well as those who may be actively developing expertise. The study used semi-structured interviews, search tasks with think-aloud narratives, and talk-after protocols. Searches were screen-captured with simultaneous audio-recording of the think-aloud narrative. Data were coded and analyzed using NVivo9 and manually. Grounded theory allowed categories and themes to emerge from the data. Categories represented conceptual knowledge and attributes of expert searchers. In accord with grounded theory method, once theoretical saturation was achieved, during the final stage of analysis the data were viewed through lenses of existing theoretical frameworks. For this study, threshold concept theory (Meyer & Land, 2003) was used to explore which concepts might be threshold concepts. Threshold concepts have been used to explore transformative learning portals in subjects ranging from economics to mathematics. A threshold concept has five defining characteristics: transformative (causing a shift in perception), irreversible (unlikely to be forgotten), integrative (unifying separate concepts), troublesome (initially counter-intuitive), and may be bounded. Themes that emerged provided evidence of four concepts which had the characteristics of threshold concepts. These were: information environment: the total information environment is perceived and understood; information structures: content, index structures, and retrieval algorithms are understood; information vocabularies: fluency in search behaviors related to language, including natural language, controlled vocabulary, and finesse using proximity, truncation, and other language-based tools. The fourth threshold concept was concept fusion, the integration of the other three threshold concepts and further defined by three properties: visioning (anticipating next moves), being light on one's 'search feet' (dancing property), and profound ontological shift (identity as searcher). In addition to the threshold concepts, findings were reported that were not concept-based, including praxes and traits of expert searchers. A model of search expertise is proposed with the four threshold concepts at its core that also integrates the traits and praxes elicited from the study, attributes which are likewise long recognized in LIS research as present in professional searchers. The research provides a deeper understanding of the transformative learning experiences involved in the acquisition of search expertise. It adds to our understanding of search expertise in the context of today's information environment and has implications for teaching advanced search, for research more broadly within library and information science, and for methodologies used to explore threshold concepts.

Learning portals : analyzing threshold concept theory for LIS education

This paper explores the theoretical framework of threshold concepts and its potential for LIS education. Threshold concepts are key ideas, often troublesome and counter-intuitive, that are critical to profound understanding of a domain. Once understood, they allow mastery of significant aspects of the domain, opening up new, previously inaccessible ways of thinking. The paper is developed in three parts. First, threshold concept theory is introduced and studies of its use in higher education are described, including emergent work related to LIS. Second, results of a recent study on learning experiences integral to learning to search are presented along with their implications for search expertise and search education, forming a case illustration of what threshold concept theory may contribute to this and other areas of LIS education. Third, the potential of threshold concept theory for LIS education is discussed. The paper concludes that threshold concept theory has much to offer LIS education, particularly for researching critical concepts and competencies, and considerations for a research agenda are put forth.

The potential of combining phenomenography, variation theory and threshold concepts to inform curriculum design in higher education

This chapter describes an innovative method of curriculum design that is based on combining phenomenographic research, and the associated variation theory of learning, with the notion of disciplinary threshold concepts to focus specialised design attention on the most significant and difficult parts of the curriculum. The method involves three primary stages: (i) identification of disciplinary concepts worthy of intensive curriculum design attention, using the criteria for threshold concepts; (ii) action research into variation in students’ understandings/misunderstandings of those concepts, using phenomenography as the research approach; (iii) design of learning activities to address the poorer understandings identified in the second stage, using variation theory as a guiding framework. The curriculum design method is inherently theory and evidence based. It was developed and trialed during a two-year project funded by the Australian Learning and Teaching Council, using physics and law disciplines as case studies. Disciplinary teachers’ perceptions of the impact of the method on their teaching and understanding of student learning were profound. Attempts to measure the impact on student learning were less conclusive; teachers often unintentionally deviated from the design when putting it into practice for the first time. Suggestions for improved implementation of the method are discussed.

A threshold analysis of dengue transmission in terms of weather variables and imported dengue cases in Australia

Dengue virus (DENV) transmission in Australia is driven by weather factors and imported dengue fever (DF) cases. However, uncertainty remains regarding the threshold effects of high-order interactions among weather factors and imported DF cases and the impact of these factors on autochthonous DF. A time-series regression tree model was used to assess the threshold effects of natural temporal variations of weekly weather factors and weekly imported DF cases in relation to incidence of weekly autochthonous DF from 1 January 2000 to 31 December 2009 in Townsville and Cairns, Australia. In Cairns, mean weekly autochthonous DF incidence increased 16.3-fold when the 3-week lagged moving average maximum temperature was <32 °C, the 4-week lagged moving average minimum temperature was ≥24 °C and the sum of imported DF cases in the previous 2 weeks was >0. When the 3-week lagged moving average maximum temperature was ≥32 °C and the other two conditions mentioned above remained the same, mean weekly autochthonous DF incidence only increased 4.6-fold. In Townsville, the mean weekly incidence of autochthonous DF increased 10-fold when 3-week lagged moving average rainfall was ≥27 mm, but it only increased 1.8-fold when rainfall was <27 mm during January to June. Thus, we found different responses of autochthonous DF incidence to weather factors and imported DF cases in Townsville and Cairns. Imported DF cases may also trigger and enhance local outbreaks under favorable climate conditions.

Visual analog scale and pressure pain threshold for delayed onset muscle soreness assessment

Objectives: To investigate the relationship between two assessments to quantify delayed onset muscle soreness [DOMS]: visual analog scale [VAS] and pressure pain threshold [PPT]. Methods: Thirty-one healthy young men [25.8 ± 5.5 years] performed 10 sets of six maximal eccentric contractions of the elbow flexors with their non-dominant arm. Before and one to four days after the exercise, muscle pain perceived upon palpation of the biceps brachii at three sites [5, 9 and 13 cm above the elbow crease] was assessed by VAS with a 100 mm line [0 = no pain, 100 = extremely painful], and PPT of the same sites was determined by an algometer. Changes in VAS and PPT over time were compared amongst three sites by a two-way repeated measures analysis of variance, and the relationship between VAS and PPT was analyzed using a Pearson product-moment correlation. Results: The VAS increased one to four days after exercise and peaked two days post-exercise, while the PPT decreased most one day post-exercise and remained below baseline for four days following exercise [p < 0.05]. No significant difference among the three sites was found for VAS [p = 0.62] or PPT [p = 0.45]. The magnitude of change in VAS did not significantly correlate with that of PPT [r = −0.20, p = 0.28]. Conclusion: These results suggest that the level of muscle pain is not region-specific, at least among the three sites investigated in the study, and VAS and PPT provide different information about DOMS, indicating that VAS and PPT represent different aspects of pain.

The Limited Benefit of Prison in Controlling Crime : On the Threshold of a Political Shift

In 2012 the New Zealand government spent $3.4 billion, or nearly $800 per person, on responses to crime via the justice system. Research shows that much of this spending does little to reduce the changes of re-offending. Relatively little money is spent on victims, the rehabilitation of offenders or to support the families of offenders. This book is based on papers presented at the Costs of Crime forum held by the Institute of Policy Studies in February 2011. It presents lessons from what is happening in Australia, Britain and the United States and focuses on how best to manage crime, respond to victims, and reduce offending in a cost-effective manner in a New Zealand context. It is clear that strategies are needed that are based on better research and a more informed approach to policy development. Such strategies must assist victims constructively while also reducing offending. Using public resources to lock as many people in our prisons as possible cannot be justified by the evidence and is fiscally unsustainable; nor does such an approach make society safer. To reduce the costs of crime we need to reinvest resources in effective strategies to build positive futures for those at risk and the communities needed to sustain them.

Photodissociation of TEMPO-modified peptides: New approaches to radical-directed dissociation of biomolecules

Radical-directed dissociation of gas phase ions is emerging as a powerful and complementary alternative to traditional tandem mass spectrometric techniques for biomolecular structural analysis. Previous studies have identified that coupling of 2-[(2,2,6,6-tetramethylpiperidin-1-oxyl)methyl] benzoic acid (TEMPO-Bz) to the N-terminus of a peptide introduces a labile oxygen-carbon bond that can be selectively activated upon collisional activation to produce a radical ion. Here we demonstrate that structurally-defined peptide radical ions can also be generated upon UV laser photodissociation of the same TEMPO-Bz derivatives in a linear ion-trap mass spectrometer. When subjected to further mass spectrometric analyses, the radical ions formed by a single laser pulse undergo identical dissociations as those formed by collisional activation of the same precursor ion, and can thus be used to derive molecular structure. Mapping the initial radical formation process as a function of photon energy by photodissociation action spectroscopy reveals that photoproduct formation is selective but occurs only in modest yield across the wavelength range (300-220 nm), with the photoproduct yield maximised between 235 and 225 nm. Based on the analysis of a set of model compounds, structural modifications to the TEMPO-Bz derivative are suggested to optimise radical photoproduct yield. Future development of such probes offers the advantage of increased sensitivity and selectivity for radical-directed dissociation. © 2014 the Owner Societies.

Ozone-induced dissociation of conjugated lipids reveals significant reaction rate enhancements and characteristic odd-electron product ions

Ozone-induced dissociation (OzID) is an alternative ion activation method that relies on the gas phase ion-molecule reaction between a mass-selected target ion and ozone in an ion trap mass spectrometer. Herein, we evaluated the performance of OzID for both the structural elucidation and selective detection of conjugated carbon-carbon double bond motifs within lipids. The relative reactivity trends for \[M + X](+) ions (where X = Li, Na, K) formed via electrospray ionization (ESI) of conjugated versus nonconjugated fatty acid methyl esters (FAMEs) were examined using two different OzID-enabled linear ion-trap mass spectrometers. Compared with nonconjugated analogues, FAMEs derived from conjugated linoleic acids were found to react up to 200 times faster and to yield characteristic radical cations. The significantly enhanced reactivity of conjugated isomers means that OzID product ions can be observed without invoking a reaction delay in the experimental sequence (i.e., trapping of ions in the presence of ozone is not required). This possibility has been exploited to undertake neutral-loss scans on a triple quadrupole mass spectrometer targeting characteristic OzID transitions. Such analyses reveal the presence of conjugated double bonds in lipids extracted from selected foodstuffs. Finally, by benchmarking of the absolute ozone concentration inside the ion trap, second order rate constants for the gas phase reactions between unsaturated organic ions and ozone were obtained. These results demonstrate a significant influence of the adducting metal on reaction rate constants in the fashion Li > Na > K.

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

Functional encryption for threshold functions (or fuzzy IBE) from lattices

Cryptosystems based on the hardness of lattice problems have recently acquired much importance due to their average-case to worst-case equivalence, their conjectured resistance to quantum cryptanalysis, their ease of implementation and increasing practicality, and, lately, their promising potential as a platform for constructing advanced functionalities. In this work, we construct “Fuzzy” Identity Based Encryption from the hardness of the Learning With Errors (LWE) problem. We note that for our parameters, the underlying lattice problems (such as gapSVP or SIVP) are assumed to be hard to approximate within supexponential factors for adversaries running in subexponential time. We give CPA and CCA secure variants of our construction, for small and large universes of attributes. All our constructions are secure against selective-identity attacks in the standard model. Our construction is made possible by observing certain special properties that secret sharing schemes need to satisfy in order to be useful for Fuzzy IBE. We also discuss some obstacles towards realizing lattice-based attribute-based encryption (ABE).

Lattice-based threshold changeability for standard shamir sectret-sharing schemes

We consider the problem of increasing the threshold parameter of a secret-sharing scheme after the setup (share distribution) phase, without further communication between the dealer and the shareholders. Previous solutions to this problem require one to start off with a nonstandard scheme designed specifically for this purpose, or to have communication between shareholders. In contrast, we show how to increase the threshold parameter of the standard Shamir secret-sharing scheme without communication between the shareholders. Our technique can thus be applied to existing Shamir schemes even if they were set up without consideration to future threshold increases. Our method is a new positive cryptographic application for lattice reduction algorithms, inspired by recent work on lattice-based list decoding of Reed-Solomon codes with noise bounded in the Lee norm. We use fundamental results from the theory of lattices (geometry of numbers) to prove quantitative statements about the information-theoretic security of our construction. These lattice-based security proof techniques may be of independent interest.

A threshold concepts focus to curriculum design: supporting student learning through application of variation theory

This project develops and evaluates a model of curriculum design that aims to assist student learning of foundational disciplinary ‘Threshold Concepts’. The project uses phenomenographic action research, cross-institutional peer collaboration and the Variation Theory of Learning to develop and trial the model. Two contrasting disciplines (Physics and Law) and four institutions (two research-intensive and two universities of technology) were involved in the project, to ensure broad applicability of the model across different disciplines and contexts. The Threshold Concepts that were selected for curriculum design attention were measurement uncertainty in Physics and legal reasoning in Law. Threshold Concepts are key disciplinary concepts that are inherently troublesome, transformative and integrative in nature. Once understood, such concepts transform students’ views of the discipline because they enable students to coherently integrate what were previously seen as unrelated aspects of the subject, providing new ways of thinking about it (Meyer & Land 2003, 2005, 2006; Land et al. 2008). However, the integrative and transformative nature of such threshold concepts make them inherently difficult for students to learn, with resulting misunderstandings of concepts being prevalent...

Differentiation of complex lipid isomers by radical-directed dissociation mass spectrometry

Contemporary lipidomics protocols are dependent on conventional tandem mass spectrometry for lipid identification. This approach is extremely powerful for determining lipid class and identifying the number of carbons and the degree of unsaturation of any acyl-chain substituents. Such analyses are however, blind to isomeric variants arising from different carbon carbon bonding motifs within these chains including double bond position, chain branching, and cyclic structures. This limitation arises from the fact that conventional, low energy collision-induced dissociation of even-electron lipid ions does not give rise to product ions from intrachain fragmentation of the fatty acyl moieties. To overcome this limitation, we have applied radical-directed dissociation (RDD) to the study of lipids for the first time. In this approach, bifunctional molecules that contain a photocaged radical initiator and a lipid-adducting group, such as 4-iodoaniline and 4-iodobenzoic acid, are used to form noncovalent complexes (i.e., adduct ions) with a lipid during electrospray ionization. Laser irradiation of these complexes at UV wavelengths (266 nm) cleaves the carbon iodine bond to liberate a highly reactive phenyl radical. Subsequent activation of the nascent radical ions results in RDD with significant intrachain fragmentation of acyl moieties. This approach provides diagnostic fragments that are associated with the double bond position and the positions of chain branching in glycerophospholipids, sphingomyelins and triacylglycerols and thus can be used to differentiate isomeric lipids differing only in such motifs. RDD is demonstrated for well-defined lipid standards and also reveals lipid structural diversity in olive oil and human very-low density lipoprotein.