Mass spectrometric study of the dissociation of Group XI metal complexes with fatty acids and glycerolipids : Ag2H+ and Cu2H+ ion formation in the presence of a double bond

Results of mass spectrometric studies are reported for the collisional dissociation of Group XI (Cu, Ag, Au) metal ion complexes with fatty acids (palmitic, oleic, linoleic and a-linolenic) and glycerolipids. Remarkably, the formation of M2H+ ions (M = Cu, Ag) is observed as a dissociation product of the ion complexes containing more than one metal cation and only if the lipid in the complex contains a double bond. Ag2H+ is formed as the main dissociation channel for all three of the fatty acids containing double bonds that were investigated while Cu2H+ is formed with one of the fatty acids and, although abundant, is not the dominant dissociation channel. Also. Cu(I) and Ag(I) ion complexes were observed with glycerolipids (including triacylglycerols and glycerophospholipids) containing either saturated or unsaturated fatty acid substituents. Interestingly. Ag2H+ ion is formed in a major fragmentation channel with the lipids that are able to form the complex with two metal cations (triacylglycerols and glycerophosphoglycerols), while lipids containing a fixed positive charge (glycerophospocholines) complex only with a single metal cation. The formation of Ag2H+ ion is a significant dissociation channel from the complex ion Ag-2(L-H)(+) where L = Glycerophospholipid (GP) (18:1/18:1). Cu(I) also forms complexes of two metal cations with glycerophospholipids but these do not produce Cu2H+ upon dissociation. Rather organic fragments, not containing Cu(I), are formed, perhaps due to different interactions of these metal cations with lipids resulting from the much smaller ionic radius of Cu(I) compared to Ag(I) (C).

Photoelectron spectroscopic study of the oxyallyl diradical

The photoelectron spectrum of the oxyallyl (OXA) radical anion has been measured. The radical anion has been generated in the reaction of the atomic oxygen radical anion (O center dot-) with acetone. Three low-lying electronic states of OXA have been observed in the spectrum. Electronic structure calculations have been performed for the triplet states (B-3(2) and B-3(1)) of OXA and the ground doublet state ((2)A(2)) of the radical anion using density, functional theory (DFT). Spectral simulations have been carried out for the triplet statics based on the results of the DFT calculations. The simulation identifies a vibrational progression of the CCC bending mode of the B-3(2) state of OXA in the lower electron binding energy (eBE) portion of the spectrum. On top of the B-3(2) feature, however, the experimental spectrum exhibits additional photoelectron peaks whose angular distribution is distinct from that for the vibronic peaks of the B-3(2) state. Complete active space self-consistent field (CASSCF) method and second-order perturbation theory based on the CASSCF wave function (CASPT2) have been employed to study the lowest singlet state ((1)A(1)) of OXA. The simulation based on the results of these electronic structure calculations establishes that the overlapping peaks represent the vibrational ground level of the (1)A(1) state and its vibrational progression of the CO stretching mode. The A, state is the lowest electronic state of,OXA, and the electron affinity (EA) of OXA is 1.940 +/- 0.010 eV. The B-3(2) state is the first excited state with an electronic term energy of 55 +/- 2 meV. The widths of the vibronic peaks of the (X) over tilde (1)A(1) state are much broader than those of the (a) over tilde B-3(2) state, implying that the (1)A(1) state is indeed a transition state. The CASSCF and CASPT2 calculations suggest that the (1)A(1) state is at a potential maximum along the nuclear coordinate representing disrotatory motion of the two methylene groups, which leads to three-membered-ring formation, i.e., cydopropanone. The simulation of (b) over tilde B-3(1) OXA reproduces the higher eBE portion of the spectrum very well. The term energy of the B-3(1) state is 0.883 +/- 0.012 eV. Photoelectron spectroscopic measurements have also been conducted for the other ion products of the O center dot- reaction with acetone. The photoelectron imaging spectrum of the acetylcarbene (AC) radical anion exhibits a broad, structureless feature, which is assigned to the (X) over tilde (3)A '' state of AC. The ground ((2)A '') and first excited ((2)A') states of the 1-methylvinoxy (1-MVO) radical have been observed in the photoelectron spectrum of the 1-MVO ion, and their vibronic structure has been analyzed.

Requiem for a beast : a case study in controversy

In 2008, Matt Ottley’s Requiem for a Beast: A Work for Image, Word and Music was awarded the Book of the Year: Picture Book by the Children’s Book Council of Australia (CBCA). Ottley’s book is challenging in its form and content: it uses words, illustrations, and music to tell a sustained, multi-layered narrative about one young man’s attempts to reconcile his family’s and his nation’s shameful history of violence against Aboriginal Australians, while also coming to terms with his own attempts to commit suicide. Given the ways in which the CBCA’s annual book awards are used by teachers, librarians, and parents to select the “best” books for young readers, it is unsurprising that the prizing of Requiem for a Beast stirred up controversy. Responses to the book proliferated across professional and popular outlets—it even received coverage on an Australian tabloid television program—and initiated a variety of conversations about what constitutes appropriate reading for young people. Perhaps more significantly, the controversy over Requiem winning picture book of the year forced the CBCA, teacher librarians, and caregivers to examine (and, often, defend) their roles and responsibilities in the circulation and promotion of children’s literature. This paper reads the Requiem controversies as a case study for understanding the complementary and contradictory roles of institutions and individuals in the ethical circulation of children’s literature in contemporary Australia and beyond.

An exploratory study for the development of emergency nurse practitioner specialist clinical practice standards

This thesis presents a mixed methods study to develop specialty specific clinical practice standards for Emergency Nurse Practitioners. This is the first time in Australia that Nurse Practitioners standards have been developed for a clinical specialty. These standards will guide educational preparation for the role and ongoing Continuous Professional Development for endorsed Emergency Nurse Practitioners.

Relating Across Difference : A Case Study in Transformative Learning

This chapter examines the process of “transformative learning” for the 2008 cohort of the St. Thomas More College���Intercordia Canada (STM/IC) international community service-learning program. My primary data comes from the eight students who were part of that cohort, when I was their program coordinator. That data later became the heart of my Master’s thesis and was approved by the Research Ethics Office of the University of Saskatchewan. In this chapter I focus on three of those eight participants, outlining the critical elements of their experiences that were conducive to their transformative learning. To be sure, my sample size is too small to draw generalizable conclusions, but the quality of information I received from these students and their colleagues, coupled with the follow-up conversations I had with other educators and with the accompanying literature, supports the value of reflecting at length here about these students’ comments. I have chosen to highlight the experiences of these three participants because together they provide a range of experiences that best enables an analysis of the conditions that both did and did not lead to transformative learning. This case study suggests that transformative learning occurs through: the dynamics of vulnerability, a discovery of persisting differences within inter-personal relationships, and an experience of welcome and hospitality in the host environment. In contrast to other studies that focus on the enhanced capacities, skills and subsequent employability of participants through international education, transformative learning for these students required a relinquishing of securities, a disorientation and critical interrogation of the self, and enhanced receptivity to the newly recognized Other. Moreover, consistent with the critical-humanistic educational philosophy shared in different ways by the participants of the STM/IC program, this study suggests that international community service-learning can most responsibly contribute to good global citizenship through the construction of relationships of solidarity across difference.

Contributions of the private sector to global biodiversity protection: case study of the Fortune 500 companies

Since the inception of the UN Convention on Biological Diversity (CBD) in 1992, little progress has been achieved in terms of involving the business community in protecting biological diversity worldwide. This article assesses the current activities of US Fortune 500 companies with respect to global biodiversity protection and the goals of the CBD. Data and information collected from 500 companies within eight major industrial sectors were further categorized at the company level to assess each company's involvement in global biodiversity protection. Our findings show that although companies' business profiles highly influence their decision-making process regarding the adoption of biodiversity protection policies and measures, their revenue profiles are less influential. We show that despite generating low revenues, companies in the utility sector are more active in the adoption of biodiversity protection policy than those in the financial sector, which generate high revenues. This study also demonstrates that companies must be convinced of the major effects of biodiversity loss on their bottom lines to be motivated to protect biological diversity. Companies' business and business-related risk profiles can also influence the adoption of biodiversity protection policies within the company. The study further demonstrates that a measurable biodiversity impact indicator is necessary for the companies to get seriously involved in the mitigation action. Finally, this study proposes a three-step biodiversity loss mitigation action framework that is drawn upon the assessment of the 500 companies that can contribute to develop an elaborative framework of business sector-specific mitigation plan. © 2013 Copyright Taylor and Francis Group, LLC.

Testing the international linkage in the platinum-group metal futures markets

This study tests whether an international market exists in the platinum-group metal (PGM) futures markets. For this purpose, we tested the law of one price (LOP) and the causality between the U.S. and Japanese platinum and palladium futures markets. We also performed the test when structural breaks are considered. Long-run price relationships were found in both platinum and palladium markets but the LOP only sustained in the palladium market. The causality test revealed that it is the U.S. market that leads the price to transmit information between the U.S. and Japanese markets. Structural breaks had large impacts on the test results, suggesting that incorporating breaks is important when investigating the international price linkage in the PGM futures markets.

A case study in flood fatality : Beijing July 2012 flood

Background The aim of this study is to examine the flood fatality with a view to identifying risks which may inform public policy responses to future flood. On July 21st, 2012, Beijing suffered the heaviest rain since 1963. The average rainfall was 215 mm over a 24 hour period in the central city (301mm in Fangshan District). The rain resulted in a flood that caused severe health, social and financial impact. Results This flood caused 79 deaths. Of the 71 deaths for which a specific cause could be identified, 5 were rescue team members, 42 were killed by drowning (11 in the car), and the others by electricity shock, fallen house, falling items and lightning. The total financial cost was estimated to be US$ 1.7 billion. The causations of the deaths inform the risks associated with the flood. Discussion This flood had a catastrophic impact on Beijing, mainly due to the intensity of the rain (the rain was the heaviest in the modern Beijing history; possibly due to global warming and urban heat island effect), the vulnerability of the infrastructure (poor standards of drainage, disorganized water management systems and decreased permeability of the earth as a result of the city’s rapid development), and the capacity of the response system (mainly dependent on the awareness of the citizens, warning systems and the capacity of the emergency rescue). Implication Many risk management measures have been implemented as a result of this flood, including water level warning marks, flood safety education and warnings sent to mobile phones, a project to move about 74,500 farmers away from the flood-prone areas within 5 years. However, further measures targeted at the fundamental issues identified by this analysis are necessary, especially those targeting at health issues. These may include better planning, improved drainage systems and ecological development to increase permeability etc..

Real or imagined? A study exploring the existence of common method variance effects in road safety research

Common method variance (CMV) has received little attention within the field of road safety research despite a heavy reliance on self-report data. Two surveys were completed by 214 motorists over a two-month period, allowing associations between social desirability and key road safety variables and relationships between scales across the two survey waves to be examined. Social desirability was found to have a strong negative correlation with the Driver Behaviour Questionnaire (DBQ) sub-scales as well as age, but not with crashes and offences. Drivers who scored higher on the social desirability scale were also less likely to report aberrant driving behaviours as measured by the DBQ. Controlling for social desirability did not substantially alter the predictive relationship between the DBQ and the crash and offences variables. The strength of the correlations within and between the two waves were also compared with the results strongly suggesting that effects associated with CMV were present. Identification of CMV would be enhanced by the replication of this study with a larger sample size and comparing self-report data with official sources.

A comparative study of the proliferation and osteogenic differentiation of human periodontal ligament cells cultured on β-TCP ceramics and demineralized bone matrix with or without osteogenic inducers in vitro

The repair of bone defects that result from periodontal diseases remains a clinical challenge for periodontal therapy. β-tricalcium phosphate (β-TCP) ceramics are biodegradable inorganic bone substitutes with inorganic components that are similar to those of bone. Demineralized bone matrix (DBM) is an acid-extracted organic matrix derived from bone sources that consists of the collagen and matrix proteins of bone. A few studies have documented the effects of DBM on the proliferation and osteogenic differentiation of human periodontal ligament cells (hPDLCs). The aim of the present study was to investigate the effects of inorganic and organic elements of bone on the proliferation and osteogenic differentiation of hPDLCs using three-dimensional porous β-TCP ceramics and DBM with or without osteogenic inducers. Primary hPDLCs were isolated from human periodontal ligaments. The proliferation of the hPDLCs on the scaffolds in the growth culture medium was examined using a Cell‑Counting kit‑8 (CCK-8) and scanning electron microscopy (SEM). Alkaline phosphatase (ALP) activity and the osteogenic differentiation of the hPDLCs cultured on the β-TCP ceramics and DBM were examined in both the growth culture medium and osteogenic culture medium. Specific osteogenic differentiation markers were examined using reverse transcription-quantitative polymerase chain reaction (RT-qPCR). SEM images revealed that the cells on the β-TCP were spindle-shaped and much more spread out compared with the cells on the DBM surfaces. There were no significant differences observed in cell proliferation between the β-TCP ceramics and the DBM scaffolds. Compared with the cells that were cultured on β-TCP ceramics, the ALP activity, as well as the Runx2 and osteocalcin (OCN) mRNA levels in the hPDLCs cultured on DBM were significantly enhanced both in the growth culture medium and the osteogenic culture medium. The organic elements of bone may exhibit greater osteogenic differentiation effects on hPDLCs than the inorganic elements.

Porohyperelastic finite element model for the kangaroo humeral head cartilage based on experimental study and the consolidation theory

Solid-extracellular fluid interaction is believed to play an important role in the strain-rate dependent mechanical behaviors of shoulder articular cartilages. It is believed that the kangaroo shoulder joint is anatomically and biomechanically similar to human shoulder joint and it is easy to get in Australia. Therefore, the kangaroo humeral head cartilage was used as the suitable tissue for the study in this paper. Indentation tests from quasi-static (10-4/sec) to moderately high strain-rate (10-2/sec) on kangaroo humeral head cartilage tissues were conduced to investigate the strain-rate dependent behaviors. A finite element (FE) model was then developed, in which cartilage was conceptualized as a porous solid matrix filled with incompressible fluids. In this model, the solid matrix was modeled as an isotropic hyperelastic material and the percolating fluid follows Darcy’s law. Using inverse FE procedure, the constitutive parameters related to stiffness, compressibility of the solid matrix and permeability were obtained from the experimental results. The effect of solid-extracellular fluid interaction and drag force (the resistance to fluid movement) on strain-rate dependent behavior was investigated by comparing the influence of constant, strain dependent and strain-rate dependent permeability on FE model prediction. The newly developed porohyperelastic cartilage model with the inclusion of strain-rate dependent permeability was found to be able to predict the strain-rate dependent behaviors of cartilages.

Adsorption thermodynamics and kinetics study for the self-assembly of 1,8,15,22-tetraaminophthalocyanatocobalt(II) on glassy carbon surface

Spontaneous adsorption of 1,8,15,22-tetraaminophthalocyanatocobalt(II) (4α-CoIITAPc) on glassy carbon (GC) electrode leads to the formation of a stable self-assembled monolayer (SAM). Since the SAM of 4α-CoIITAPc is redox active, its adsorption on GC electrode was followed by cyclic voltammetry. SAM of 4α-CoIITAPc on GC electrode shows two pairs of well-defined redox peaks corresponding to CoIII/CoII and CoIIIPc−1/CoIIIPc−2. The surface coverage (Γ) value, calculated by integrating the charge under CoII oxidation, was used to study the adsorption thermodynamics and kinetics of 4α-CoIITAPc on GC surface. Cyclic voltammetric studies show that the adsorption of 4α-CoIITAPc on GC electrode has reached the saturation coverage (Γs) within 3 h. The Γs value for the SAM of 4α-CoIITAPc on GC electrode was found to be 2.37 × 10−10 mol cm−2. Gibbs free energy (ΔGads) and adsorption rate constant (kad) for the adsorption of 4α-CoIITAPc on GC surface were found to be −16.76 kJ mol−1 and 7.1 M−1 s−1, respectively. The possible mechanism for the self-assembly of 4α-CoIITAPc on GC surface is through the addition of nucleophilic amines to the olefinic bond on the GC surface in addition to a meager contribution from π stacking. The contribution of π stacking was confirmed from the adsorption of unsubstituted phthalocyanatocobalt(II) (CoPc) on GC electrode. Raman spectra for the SAM of 4α-CoIITAPc on carbon surface shows strong stretching and breathing bands of Pc macrocycle, pyrrole ring and isoindole ring. Raman and CV studies suggest that 4α-CoIITAPc is adopting nearly a flat orientation or little bit tilted orientation.

Are empowered women more likely to deliver in facilities? An explorative study using the Nepal Demographic and Health Survey 2011

Development literature has argued that empowering women can effectively increase the utilisation of maternal health care. This study examines this hypothesis in the context of Nepal where only 28% of women delivered in facilities. The two-level random intercept logit models were fitted for data from the Nepal Demographic and Health Surveys 2011. Women‟s empowerment was quantified with a single index constructed from many variables. These variables captured different aspects of women‟s lives and decision-making in their households, and were combined using the principal component analysis method. The results confirmed a positive relationship between women‟s as an inevitable product of the economic development process.

Do e-learning applications click with students globally? A study of the development and adoption of WriteCite.com

This paper traces the process of invention of adoption of WriteCite.com which is an internet based learning tool used by students to format citation lists. A number of theoretical issues relating to development and deployment of online learning tools are addressed in this paper. A significant finding in this paper is that adoption rate of new technologies amongst students, in this case for WriteCite.com, is not immediately global in nature despite the internet's ubiquity and the existence of internationally accepted bibliographic styles. Rather, and in contrast to neo theories of technology internationalisation, early-stage adoption tends to be geo-centric and concentrated in the US. In the case of WriteCite.com, which has not been sponsored by an academic institution, the findings reflect voluntary rates of globa adoption. From an applied perspective, the process of identifying globally contestable markets is relevant to developers of online learning tools.