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    Planar chiral oxazolines based on [2.2]paracyclophane : a new toolbox for asymmetric synthesis : a thesis presented in partial fulfilment of the requirements for the degree of Doctor of Philosophy in Chemistry at Massey University, Manawatū, New Zealand
    (Massey University, 0024-03-07) Tewari, Shashank
    This thesis contains total 7 chapters, dealing with the synthesis of planar chiral Oxazolines based on [2.2]paracyclophane, enantiopure products obtained from their resolution, synthesis of metal-based chiral complexes, studies on C-H activation field, namely selective remote β-C-H activation of cyclic amines, and future ideas towards the goal. As the main focus of this thesis is on the development of novel planar chiral [2.2]paracyclophane derivatives, Chapter 1 starts with a brief description of [2.2]paracyclophane chemistry. A short introduction about the synthesis of key enantioenriched [2.2]paracyclophane derivatives is given. Finally, a short introduction of the recent applications of [2.2]paracyclophane-based ligands in asymmetric catalysis is also mentioned. Chapter 2 outlines a brief overview of the role of 2-oxazolines. 2-Oxazolines have been utilized in the field of asymmetric catalysis as ligands and chiral auxiliaries. The chapter briefly discusses the synthesis and highlights some of the uses of 2-oxazolines as chiral ligands. Chapter 3 describes the concise synthesis of planar chiral oxazolines based on [2.2]paracyclophanes. Various oxazoline-based compounds that were synthesized are all discussed in Chapter 3. The synthesis of mono-oxazolines coupled to [2.2]paracyclophanes, based on the methodology developed in our lab was accomplished. The next were the synthesis of bis-oxazolines and tetra-oxazolines coupled to [2.2]paracyclophane. The chapter mentions all the details and substrate scope generated with oxazolines. Chapter 4 focuses on the resolution of [2.2]paracycoplane by the hydrolysis of the oxazolines. The enantiopure products like planar chiral mono-acids, bis-acids, and partial acids were obtained by hydrolysis of the oxazolines. Apart from them, a section in the chapter describes the decarboxylative phosphorylation that was achieved through our planar chiral acids. Synthesis of planar chiral diamines via Curtius rearrangement of the diacids is also described in the chapter, followed by phanol synthesis. A part of the above chapter describes about the rhodium paddle-wheel complex formed by partial chiral acids. An attempt to make dinuclear gold complexes was made that was also successful. Overall, chapter four is the highlight of the thesis, where a lot of pure chiral products are made and their utility is explained in the field of asymmetric catalysis. Chapter 5 describes the remote β-C-H activation of cyclic amines. Attempts were made to accomplish the functionalization through the directing group strategy. The directing groups based on heterocyclic piperidine and cyclic amines were synthesized successfully. These pre-made directing groups were used for the C-H bond functionalization but the functionalization possessed many challenges that made the functionalization difficult. Chapter 6 explains the future scope of the research work mentioned in this thesis. Finally, Chapter 7 describes the experimental procedures and characterization of the synthesized compounds mentioned in Chapters 3 to 5.
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    The Supervisor
    (World Scientific Publishing, 1/01/1997) Sligo F
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    Mathematical modelling of anoestrus in dairy cows and the linkage to nutrition
    (1/01/2005) Smith, JF; Soboleva, TK; Peterson, AJ; Pleasants, T; Chagas, LM; Burke, CR
    Postpartum anoestrus is a major reproductive problem in New Zealand dairy cows and its duration is related to the nutrition levels both pre and post calving. However, the mechanistic details of this relationship are largely unknown. A better understanding of the interactions between nutritional status, and the levels of the reproductive hormones controlling follicle development and ovulation is needed. A mathematical model consisting of a set of interactive nonlinear differential equations and describing the dynamics of the interactions among luteinising hormone (LH), follicle stimulating hormone (FSH) and oestradiol was developed. The model depicts oestradiol profiles generated by individual follicles from the first follicular wave after calving until ovulation, and changes in LH pulsatility leading to the first pre-ovulatory surge are also produced. The robustness of the model was ascertained from iterative processes, and it was also checked against existing experimental data so as to mimic observed changes in hormone levels. It was shown that two mathematical parameters which control: i) the speed of changes in the feedback of LH activity to oestradiol; and, ii) the sensitivity of the ovarian response to LH, have the greatest effect on duration of anoestrus.
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    All the world wide web's a stage: The performance of identity in online social networks
    (1/01/2009) Pearson E
    This paper discusses how ideas of performance can be used to conceptualize the play of identity formation on social networking sites (SNS). Linking Goffman's theories of social performance with Granovetter's notion of the social tie, this paper will argue that identities on SNS are deliberately constructed performances that straddle the frontstage and the backstage, the public and the private, and in doing so both support and rely upon webs of social connections which engage with fluid or playful identity constructions.
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    Transverse-momentum and pseudorapidity distributions of charged hadrons in pp collisions at √s = 0.9 and 2.36TeV
    (SPRINGER, 1/01/2010) Khachatryan V; Sirunyan AM; Tumasyan A; Adam W; Bergauer T; Dragicevic M; Erö J; Friedl M; Frühwirth R; Ghete VM; Hammer J; Hänsel S; Hoch M; Hörmann N; Hrubec J; Jeitler M; Kasieczka G; Krammer M; Liko D; Mikulec I; Pernicka M; Rohringer H; Schöfbeck R; Strauss J; Taurok A; Teischinger F; Waltenberger W; Walzel G; Widl E; Wulz CE; Mossolov V; Shumeiko N; Suarez Gonzalez J; Benucci L; De Wolf EA; Hashemi M; Janssen X; Maes T; Mucibello L; Ochesanu S; Rougny R; Selvaggi M; Van Haevermaet H; Van Mechelen P; Van Remortel N; Adler V; Beauceron S; D’Hondt J; Devroede O; Kalogeropoulos A; Maes J; Mozer MU; Tavernier S; Van Doninck W; Van Mulders P; Villella I; Chabert EC; Charaf O; Clerbaux B; De Lentdecker G; Dero V; Gay APR; Hammad GH; Marage PE; Vander Velde C; Vanlaer P; Wickens J; Grunewald M; Klein B; Marinov A; Ryckbosch D; Thyssen F; Tytgat M; Vanelderen L; Verwilligen P; Walsh S; Basegmez S; Bruno G; Caudron J; Cortina Gil E; De Favereau De Jeneret J; Delaere C; Demin P; Favart D; Giammanco A; Grégoire G; Hollar J; Lemaitre V; Maltoni F; Militaru O; Ovyn S; Piotrzkowski K; Quertenmont L; Schul N; Beliy N; Caebergs T; Daubie E; Herquet P; Alves GA; Pol ME
    Measurements of inclusive charged-hadron transverse-momentum and pseudorapidity distributions are presented for proton-proton collisions at √s = 0.9 and 2.36 TeV. The data were collected with the CMS detector during the LHC commissioning in December 2009. For non-single-diffractive interactions, the average charged-hadron transverse momentum is measured to be 0:46 ± 0:01 (stat.) ± 0.01 (syst.) GeV/c at 0.9 TeV and 0:50 ± 0:01 (stat.) ± 0.01 (syst.) GeV/c at 2.36 TeV, for pseudorapidities between -2:4 and +2:4. At these energies, the measured pseudorapidity densities in the central region, dNch/dη| |η|>0.5, are 3:48±0:02 (stat.) ± 0.13 (syst.) and 4:47±0:04 (stat.) ± 0.16 (syst.), respectively. The results at 0.9 TeV are in agreement with previous measurements and con- firm the expectation of near equal hadron production in pp̄ and pp collisions. The results at 2.36 TeV represent the highest-energy measurements at a particle collider to date.
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    Measurement of the charge ratio of atmospheric muons with the CMS detector
    (ELSEVIER SCIENCE BV, 1/01/2010) Khachatryan V; Sirunyan AM; Tumasyan A; Adam W; Bergauer T; Dragicevic M; Erö J; Fabjan C; Friedl M; Frühwirth R; Ghete VM; Hammer J; Hänsel S; Hoch M; Hörmann N; Hrubec J; Jeitler M; Kasieczka G; Kiesenhofer W; Krammer M; Liko D; Mikulec I; Pernicka M; Rohringer H; Schöfbeck R; Strauss J; Taurok A; Teischinger F; Waltenberger W; Walzel G; Widl E; Wulz CE; Mossolov V; Shumeiko N; Suarez Gonzalez J; Benucci L; Ceard L; De Wolf EA; Hashemi M; Janssen X; Maes T; Mucibello L; Ochesanu S; Roland B; Rougny R; Selvaggi M; Van Haevermaet H; Van Mechelen P; Van Remortel N; Adler V; Beauceron S; Blyweert S; D'Hondt J; Devroede O; Kalogeropoulos A; Maes J; Maes M; Tavernier S; Van Doninck W; Van Mulders P; Villella I; Chabert EC; Charaf O; Clerbaux B; De Lentdecker G; Dero V; Gay APR; Hammad GH; Marage PE; Vander Velde C; Vanlaer P; Wickens J; Costantini S; Grunewald M; Klein B; Marinov A; Ryckbosch D; Thyssen F; Tytgat M; Vanelderen L; Verwilligen P; Walsh S; Zaganidis N; Basegmez S; Bruno G; Caudron J; De Favereau De Jeneret J; Delaere C; Demin P; Favart D; Giammanco A; Grégoire G; Hollar J; Lemaitre V; Militaru O; Ovyn S; Pagano D; Pin A; Piotrzkowski K; Quertenmont L
    We present a measurement of the ratio of positive to negative muon fluxes from cosmic ray interactions in the atmosphere, using data collected by the CMS detector both at ground level and in the underground experimental cavern at the CERN LHC. Muons were detected in the momentum range from 5 GeV/. c to 1 TeV/. c. The surface flux ratio is measured to be 1.2766±0.0032(stat.)±0.0032(syst.), independent of the muon momentum, below 100 GeV/. c. This is the most precise measurement to date. At higher momenta the data are consistent with an increase of the charge ratio, in agreement with cosmic ray shower models and compatible with previous measurements by deep-underground experiments. © 2010.
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    Application of equity sensitivity theory to problem-solving approaches in construction dispute negotiation
    (1/01/2011) Yiu TW; Keung CW; Wong KL
    This study applies equity sensitivity theory to investigate how the sensitivity of negotiators to perceived equity or inequity varies with their perception of the adoption of problem-solving approaches (PSAs) in negotiation in the construction industry. Drawing upon this theory, we identify three classes of negotiators: benevolents (known as "givers"), equity sensitives, and entitleds (known as "takers"). Our results suggest that most of the negotiators in our sample are entitleds. The study also provides statistical evidence that the perception of the adoption of PSAs appears to be associated with the degree of equity sensitivity of negotiators. For instance, benevolents demonstrate a significantly stronger preference for the adoption of PSAs and are thus able to obtain a higher level of negotiation satisfaction compared to the other types of negotiators. These findings are particularly relevant to the corporate managers of construction organizations, who may want to consider the inherent equity sensitivity traits of their negotiators before sending them to the negotiating table. © 2011 ASCE.
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    The economic impact of capital expenditures: Environmental regulatory delay as a source of competitive advantage?
    (1/01/2013) Wirth C; Chi J; Young M
    This study tests the proposal that by undertaking voluntary capital expenditures that are subject to lengthy environmental regulatory delays, listed companies can gain a competitive advantage. The stock market is found to react positively to new capital expenditure announcements when projects are expected to experience long delays in obtaining environmental regulatory approval. Two sources of potential competitive advantage are firm learning and first mover advantages. Lengthy delays in regulatory processes and high compliance costs incurred for environmentally-sensitive projects may allow firms opportunities to develop specialised capabilities and/or to deter industry competitors and new entrants, resulting in greater expected project NPVs. The findings also underscore the importance of non-financial environmental information to investors in their assessment of firm value. © 2013 Blackwell Publishing Ltd.
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    Biotic impacts of energy development from shale: Research priorities and knowledge gaps
    (ECOLOGICAL SOC AMER, 1/01/2014) Souther S; Tingley MW; Popescu VD; Hayman DTS; Ryan ME; Graves TA; Hartl B; Terrell K
    Although shale drilling operations for oil and natural gas have increased greatly in the past decade, few studies directly quantify the impacts of shale development on plants and wildlife. We evaluate knowledge gaps related to shale development and prioritize research needs using a quantitative framework that includes spatial and temporal extent, mitigation difficulty, and current level of understanding. Identified threats to biota from shale development include: surface and groundwater contamination; diminished stream flow; stream siltation; habitat loss and fragmentation; localized air, noise, and light pollution; climate change; and cumulative impacts. We find the highest research priorities to be probabilistic threats (underground chemical migration; contaminant release during storage, during disposal, or from accidents; and cumulative impacts), the study of which will require major scientific coordination among researchers, industry, and government decision makers. Taken together, our research prioritization outlines a way forward to better understand how energy development affects the natural world. © The Ecological Society of America.
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    Expert opinion? A micro-analysis of eating disorder talk on Dr. Phil
    (1/01/2014) LaMarre A; Sutherland O
    In this study, we explored how eating and identities of individuals diagnosed with eating disorders are constructed on a popular television talk show, Dr. Phil. Informed by conversation analytic and discursive psychological research traditions, we show how Dr. Phil, jointly with guests, constitutes guests as mentally ill and accountable for their illness. Specifically, we highlight Dr. Phil’s unilateral pursuit of a solution to the “puzzle” of the eating disorder, including its origins and meanings, as he enlists the guests’ endorsement of his versions of their situations and experiences. We examine broader implications of such a framing for societal understandings of the subjectivity of individuals diagnosed with eating disorders. Keywords: Eating Disorders, Mental Illness, Conversation Analysis, Discursive Psychology, Mass Media, Talk Television.
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    Evaluating edge-of-range genetic patterns for tropical echinoderms, Acanthaster planci and Tripneustes gratilla, of the Kermadec Islands, southwest Pacific
    (ROSENSTIEL SCH MAR ATMOS SCI, 1/01/2014) Liggins L; Gleeson L; Riginos C
    Edge-of-range populations are often typified by patterns of low genetic diversity and high genetic differentiation relative to populations within the core of a species range. The "core-periphery hypothesis," also known as the "central-marginal hypothesis," predicts that these genetic patterns at the edge-of-range are a consequence of reduced population size and connectivity toward a species range periphery. It is unclear, however, how these expectations relate to high dispersal marine species that can conceivably maintain high abundance and high connectivity at their range edge. In the present study, we characterize the genetic patterns of two tropical echinoderm populations in the Kermadec Islands, the edge of their southwest Pacific range, and compare these genetic patterns to those from populations throughout their east Indian and Pacific ranges. We find that the populations of both Acanthaster planci (Linnaeus, 1758) and Tripneustes gratilla (Linnaeus, 1758) are represented by a single haplotype at the Kermadec Islands (based on mitochondrial cytochrome oxidase C subunit I). Such low genetic diversity concurs with the expectations of the "core-periphery hypothesis." Furthermore, the haplotypic composition of both populations suggests they have been founded by a small number of colonists with little subsequent immigration. Thus, local reproduction and self-recruitment appear to maintain these populations despite the ecologically marginal conditions of the Kermadec Islands for these tropical species. Understanding rates of self-recruitment vs reliance on connectivity with populations outside of the Kermadec Islands has implications for the persistence of these populations and range stability of these echinoderm species.© 2014 Rosenstiel School of Marine and Atmospheric Science of the University of Miami.
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    Erratum: Detangling flat bands into Fano lattices
    (EPL ASSOCIATION, EUROPEAN PHYSICAL SOCIETY, 1/01/2014) Flach S; Leykam D; Bodyfelt JD; Matthies P; Desyatnikov AS
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    Return of the ghosts of dispersal past: Historical spread and contemporary gene flow in the blue sea star Linckia laevigata
    (ROSENSTIEL SCH MAR ATMOS SCI, 1/01/2014) Crandall ED; Treml EA; Liggins L; Gleeson L; Yasuda N; Barber PH; Wörheide G; Riginos C
    Marine animals inhabiting the Indian and Pacific oceans have some of the most extensive species ranges in the world, sometimes spanning over half the globe. These Indo-Pacific species present a challenge for study with both geographic scope and sampling density as limiting factors. Here, we augment and aggregate phylogeographic sampling of the iconic blue sea star, Linckia laevigata Linnaeus, 1758, and present one of the most geographically comprehensive genetic studies of any Indo-Pacific species to date, sequencing 392 base pairs of mitochondrial COI from 791 individuals from 38 locations spanning over 14,000 km. We first use a permutation based multiple-regression approach to simultaneously evaluate the relative influence of historical and contemporary gene flow together with putative barriers to dispersal. We then use a discrete diffusion model of phylogeography to infer the historical migration and colonization routes most likely used by L. laevigata across the Indo-Pacific. We show that estimates of genetic structure have a stronger correlation to geographic distances than to "oceanographic" distances from a biophysical model of larval dispersal, reminding us that population genetic estimates of gene flow and genetic structure are often shaped by historical processes. While the diffusion model was equivocal about the location of the mitochondrial most recent common ancestor (MRC A), we show that gene flow has generally proceeded in a step-wise manner across the Indian and Pacific oceans. We do not find support for previously described barriers at the Sunda Shelf and within Cenderwasih Bay. Rather, the strongest genetic disjunction is found to the east of Cenderwasih Bay along northern New Guinea. These results underscore the importance of comprehensive range-wide sampling in marine phylogeography.© 2014 Rosenstiel School of Marine and Atmospheric Science of the University of Miami.
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    Multiplicities and the subject: Rethinking a mix-of-attributes approach in the digital world
    (University of Southern California, Annenberg School for Communication & Journalism, 1/01/2015) Pearson EE; Elliot G
    It has been 30 years since Clark made his call to focus on fundamental structures of media rather than media formats (such as radio or television) and more than 10 years since Eveland proposed a mix-of-attributes approach to media effects. This article suggests that it is time for a reevaluation of the mix-of-attributes approach, noting that there is a continued focus on format when studying media content. We argue for rethinking the assumptions that preempt a mix-of-attributes approach. As a way of accounting for the complexities of how messages move in the digital media ecology, beyond the constraints of singular media formats, we first invoke the concept of multiplicities (concurrent engagement with multiple information sources) and then propose that the role of the subject be foregrounded within a revised mix-of-attributes approach to studying media effects in the digital age.
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    Genomic signatures of cooperation and conflict in the social amoeba
    (1/01/2015) Ostrowski EA; Shen Y; Tian X; Sucgang R; Jiang H; Qu J; Katoh-Kurasawa M; Brock DA; Dinh C; Lara-Garduno F; Lee SL; Kovar CL; Dinh HH; Korchina V; Jackson LR; Patil S; Han Y; Chaboub L; Shaulsky G; Muzny DM; Worley KC; Gibbs RA; Richards S; Kuspa A; Strassmann JE; Queller DC
    © 2015 Elsevier Ltd. Summary Cooperative systems are susceptible to invasion by selfish individuals that profit from receiving the social benefits but fail to contribute. These so-called "cheaters" can have a fitness advantage in the laboratory, but it is unclear whether cheating provides an important selective advantage in nature. We used a population genomic approach to examine the history of genes involved in cheating behaviors in the social amoeba Dictyostelium discoideum, testing whether these genes experience rapid evolutionary change as a result of conflict over spore-stalk fate. Candidate genes and surrounding regions showed elevated polymorphism, unusual patterns of linkage disequilibrium, and lower levels of population differentiation, but they did not show greater between-species divergence. The signatures were most consistent with frequency-dependent selection acting to maintain multiple alleles, suggesting that conflict may lead to stalemate rather than an escalating arms race. Our results reveal the evolutionary dynamics of cooperation and cheating and underscore how sequence-based approaches can be used to elucidate the history of conflicts that are difficult to observe directly.
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    Foregrounding knowledge in e-learning design: An illustration in a museum setting
    (1/01/2015) Carvalho L; Dong A; Maton K
    The nature of knowledge, and the various forms knowledge may take, is a neglected aspect of the development of e-learning environments. This paper uses Legitimation Code Theory (LCT) to conceptualise the organising principles of knowledge practices. As we will illustrate, when it comes to the design of e-learning, the organising principles of the knowledge comprising the subject area, matters as much as the content. Drawing on one dimension of LCT, Specialisation, we show how to identify and apply organising principles of knowledge, in two successive stages, through an example of our own recent work developing an e-learning environment called Design Studio. First, an analytic stage explored knowledge practices within four design disciplines, engineering, architecture, digital media, and fashion design, in terms of their organising principles. Second, a generative stage involved the creation of content for the Design Studio software as well as its look and feel, and interaction design elements, all of which were designed to be consistent with the output from the analytic stage. Design Studio was then pilot-tested by 14 high school students. The paper concludes with some general observations about how LCT can improve the creation of other e-learning environments. Australasian Journal of Educational Technology.
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    Czech youth summer camps: More than playing games in nature.
    (1/01/2016) Frainšic M; Turčová I; Martin AJ
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    Factors influencing online learning in an organisational context
    (1/01/2016) Montgomerie K; Edwards M; Thorn K
    Purpose: The purpose of this paper is to understand the factors perceived to influence successful online learning in organisations. Design/methodology/approach: Utilising an exploratory, qualitative approach, 20 participants were involved in semi-structured interviews before, during and after their involvement in an online development programme. Findings: Key factors perceived to influence participants’ learning, in order of their perceived influence, are online considerations (such as time allocation and discipline), peer support and technical delivery. Organisational culture was also found to have some influence, however further research is required to establish the extent this influence. The compounding or mitigating effect of the interplays of these factors was highlighted. Research limitations/implications: Although the study is limited by its small sample, it provides a basis for the further exploration of online learning in an organisational context and draws attention to the effect of the interplay of factors affecting learning. Research into the longitudinal influence of online learning in organisations, and particularly research which enables breakdown by learning style may assist in the development of programmes suitable for most participants. Originality/value: Online learning is becoming a common tool for employee development in the workplace and yet little is known about the factors that influence learning in this environment. This paper offers new insights into that gap through a progressive evaluation of factors facilitating or inhibiting online learning.