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

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

Negotiating the creative and the critical : Paul Dawson’s creative writing and the new humanities

In the first Modern Language Association newsletter for 2006, renowned poetry critic and MLA President, Marjorie Perloff, remarked on the growing ascendency of Creative Writing within English Studies in North America. In her column, Perloff notes that "[i]n studying the English Job Information List (JIL) so as to advise my own students and others I know currently on the market, I noticed what struck me as a curious trend: there are, in 2005, almost three times as many positions in creative writing as in the study of twentieth-century literature" (3). The dominance of Creative Writing in the English Studies job list in turn reflects the growing student demand for undergraduate and postgraduate degrees in the field—over the past 20 years, BA and MA degrees in Creative Writing in North American tertiary institutions have quadrupled (3)...

Quantum direct secret sharing with efficient eavesdropping-check and authentication based on distributed fountain codes

We propose to use a simple and effective way to achieve secure quantum direct secret sharing. The proposed scheme uses the properties of fountain codes to allow a realization of the physical conditions necessary for the implementation of no-cloning principle for eavesdropping-check and authentication. In our scheme, to achieve a variety of security purposes, nonorthogonal state particles are inserted in the transmitted sequence carrying the secret shares to disorder it. However, the positions of the inserted nonorthogonal state particles are not announced directly, but are obtained by sending degrees and positions of a sequence that are pre-shared between Alice and each Bob. Moreover, they can confirm that whether there exists an eavesdropper without exchanging classical messages. Most importantly, without knowing the positions of the inserted nonorthogonal state particles and the sequence constituted by the first particles from every EPR pair, the proposed scheme is shown to be secure.

The importance of understanding student learning styles in accounting degree programs

Accounting education is critical and any improvements in tertiary education of accounting students should result in better prepared graduates entering the profession. This study evaluates accounting students’ learning styles and the interaction of learning styles and teaching methodologies during degree programmes. Nine classes of accounting students (648 students) spread across four years and two degree programmes were evaluated. Students self-evaluated their learning style, pre-instruction. They were then subject to two separate teaching techniques (one active and one passive) in each course. Learning styles were then re-assessed and teaching techniques evaluated. Accounting students displayed a preference for passive learning, even those far advanced in their degrees. Furthermore, when learning styles matched teaching methods used, usefulness was assessed as high but when learning styles and teaching methods differed, usefulness deteriorated. Overall, the teaching methods were deemed more effective by active rather than passive learners. The implications are significant. To maximise educational benefit for the accounting profession, student learning styles should be assessed before designing appropriate teaching methodologies. This has resource implications which would have to be considered.

Questions of Science [third edition]

Table of Contents Timeline of Thinkers Timeline of Thoughts Evolution of Science Chapter 1. Introduction Chapter 2. Humans: the measure of all things Chapter 3. Men with beards: long beards Chapter 4. I doubt it Chapter 5. With good reason Chapter 6. Here be dragons Chapter 7. Stirrings of science Chapter 8. Degrees of separation Chapter 9. The Greek legacy Chapter 10. A scientific focus Chapter 11. Questions of science Chapter 12. Creatures of habit Chapter 13. A scientific method Chapter 14. Outside the square Chapter 15. Probably Chapter 16. Human, all too human Chapter 17. Cultures of science Chapter 18. 21st Century Science Chapter 19. Science in question Chapter 20. How do we know? Chapter 21. Sources

Higher Education and Sustainable Development : A Model for Curriculum Renewal

Responding to the global and unprecedented challenge of capacity building for twenty-first century life, this book is a practical guide for tertiary education institutions to quickly and effectively renew the curriculum towards education for sustainable development. The book begins by exploring why curriculum change has been so slow. It then describes a model for rapid curriculum renewal, highlighting the important roles of setting timeframes, formal and informal leadership, and key components and action strategies. The second part of the book provides detailed coverage of six core elements that have been trialled and peer reviewed by institutions around the world: - raising awareness among staff and students - mapping graduate attributes - auditing the curriculum - developing niche degrees, flagship courses and fully integrated programs - engaging and catalysing community and student markets - integrating curriculum with green campus operations. With input from more than seventy academics and grounded in engineering education experiences, this book will provide academic staff with tools and insights to rapidly align program offerings with the needs of present and future generations of students.

Factor Five : Transforming the Global Economy through 80% Improvements in Resource Productivity

The 21st century will see monumental change. Either the human race will use its knowledge and skills and change the way it interacts with the environment, or the environment will change the way it interacts with its inhabitants. In the first case, the focus of this book, we would see our sophisticated understanding in areas such as physics, chemistry, engineering, biology, planning, commerce, business and governance accumulated over the last 1,000 years brought to bear on the challenge of dramatically reducing our pressure on the environment. The second case however is the opposite scenario, involving the decline of the planet’s ecosystems until they reach thresholds where recovery is not possible, and following which we have no idea what happens. For instance, if we fail to respond to Sir Nicolas Stern’s call to meet appropriate stabilisation trajectories for greenhouse gas emissions, and we allow the average temperature of our planets surface to increase by 4-6 degrees Celsius, we will see staggering changes to our environment, including rapidly rising sea level, withering crops, diminishing water reserves, drought, cyclones, floods… allowing this to happen will be the failure of our species, and those that survive will have a deadly legacy. In this update to the 1997 International Best Seller, Factor Four, Ernst von Weizsäcker again leads a team to present a compelling case for sector wide advances that can deliver significant resource productivity improvements over the coming century. The purpose of this book is to inspire hope and to then inform meaningful action in the coming decades to respond to the greatest challenge our species has ever faced – that of living in harmony with our planet and its other inhabitants.

Energy Transformed : Building Capacity in the Engineering Profession in Australia

Global pressures of burgeoning population growth and consumption are threatening efforts to reduce negative environmental pressures associated with development such as atmospheric, land and water pollution. For example, the world’s population is now growing at over 70 million per year or 1 billion per decade (Brown, 2007), increasing from 3.5 billion in 1970, to 5 billion in 1990, to 7 billion by 2010 (United Nations, 2002). In 1990 only 13 percent of the global population lived in cities, while in 2007 more than half did. More than 60 percent of the global population lives within 100 kilometers of the coastline (World Resources Institute, 2005) and nearly all of the population growth hereon is forecast to happen in developing countries (Postel, 1999). Future levels of stress on the global environment are therefore likely to increase if current trends are used for forecasting, which is particularly challenging as scientists are already observing significant signs of degradation and failure in environmental systems. For example, the Intergovernmental Panel on Climate Change Fourth Assessment Report (IPCC, 2007) provided an nequivocal link between climate change and current human activities, in particular: the burning of fossil fuels; deforestation and land clearing; the use of synthetic greenhouse gases; and decomposition of wastes from landfill. The UK Stern Review concluded that within our lifetime there is between a 77 to 99 percent chance (depending on the climate model used) of the global average temperature rising by more than 2 degrees Celsius (Stern, 2006), with a likely greenhouse gas concentration in the atmosphere of 550 parts per million (ppm) or more by around 2100.

Fragmentation pathways of 2,3-dimethyl-2,3-dinitrobutane cations in the gas phase

2,3-Dimethyl-2,3-dinitrobutane (DMNB) is an explosive taggant added to plastic explosives during manufacture making them more susceptible to vapour-phase detection systems. In this study, the formation and detection of gas-phase \[M+H](+), \[M+Li](+), \[M+NH(4)](+) and \[M+Na](+) adducts of DMNB was achieved using electrospray ionisation on a triple quadrupole mass spectrometer. The \[M+H](+) ion abundance was found to have a strong dependence on ion source temperature, decreasing markedly at source temperatures above 50 degrees C. In contrast, the \[M+Na](+) ion demonstrated increasing ion abundance at source temperatures up to 105 degrees C. The relative susceptibility of DMNB adduct ions toward dissociation was investigated by collision-induced dissociation. Probable structures of product ions and mechanisms for unimolecular dissociation have been inferred based on fragmentation patterns from tandem mass (MS/MS) spectra of source-formed ions of normal and isotopically labelled DMNB, and quantum chemical calculations. Both thermal and collisional activation studies suggest that the \[M+Na](+) adduct ions are significantly more stable toward dissociation than their protonated analogues and, as a consequence, the former provide attractive targets for detection by contemporary rapid screening methods such as desorption electrospray ionisation mass spectrometry. Copyright (C) 2009 Commonwealth of Australia. Published by John Wiley & Sons, Ltd.

Nonlinear container ship model for the study of parametric roll resonance

Parametric roll is a critical phenomenon for ships, whose onset may cause roll oscillations up to +-40 degrees, leading to very dangerous situations and possibly capsizing. Container ships have been shown to be particularly prone to parametric roll resonance when they are sailing in moderate to heavy head seas. A Matlab/Simulink parametric roll benchmark model for a large container ship has been implemented and validated against a wide set of experimental data. The model is a part of a Matlab/Simulink Toolbox (MSS, 2007). The benchmark implements a 3rd-order nonlinear model where the dynamics of roll is strongly coupled with the heave and pitch dynamics. The implemented model has shown good accuracy in predicting the container ship motions, both in the vertical plane and in the transversal one. Parametric roll has been reproduced for all the data sets in which it happened, and the model provides realistic results which are in good agreement with the model tank experiments.

Improved healing of large segmental defects in the rat femur by reverse dynamization in the presence of bone morphogenetic protein-2

Background Large segmental defects in bone do not heal well and present clinical challenges. This study investigated modulation of the mechanical environment as a means of improving bone healing in the presence of bone morphogenetic protein (BMP)-2. Although the influence of mechanical forces on the healing of fractures is well established, no previous studies, to our knowledge, have described their influence on the healing of large segmental defects. We hypothesized that bone-healing would be improved by initial, low-stiffness fixation of the defect, followed by high-stiffness fixation during the healing process. We call this reverse dynamization. Methods A rat model of a critical-sized femoral defect was used. External fixators were constructed to provide different degrees of stiffness and, importantly, the ability to change stiffness during the healing process in vivo. Healing of the critical-sized defects was initiated by the implantation of 11 mg of recombinant human BMP (rhBMP)-2 on a collagen sponge. Groups of rats receiving BMP-2 were allowed to heal with low, medium, and high-stiffness fixators, as well as under conditions of reverse dynamization, in which the stiffness was changed from low to high at two weeks. Healing was assessed at eight weeks with use of radiographs, histological analysis, microcomputed tomography, dual x-ray absorptiometry, and mechanical testing. Results Under constant stiffness, the low-stiffness fixator produced the best healing after eight weeks. However, reverse dynamization provided considerable improvement, resulting in a marked acceleration of the healing process by all of the criteria of this study. The histological data suggest that this was the result of intramembranous, rather than endochondral, ossification. Conclusions Reverse dynamization accelerated healing in the presence of BMP-2 in the rat femur and is worthy of further investigation as a means of improving the healing of large segmental bone defects. Clinical Relevance These data provide the basis of a novel, simple, and inexpensive way to improve the healing of critical-sized defects in long bones. Reverse dynamization may also be applicable to other circumstances in which bonehealing is problematic.

Regulation and integral control of an underactuated robotic system using IDA-PBC with dynamic extension

This paper proposes a method for design of a set-point regulation controller with integral action for an underactuated robotic system. The robot is described as a port-Hamiltonian system, and the control design is based on a coordinate transformation and a dynamic extension. Both the change of coordinates and the dynamic extension add extra degrees of freedom that facilitate the solution of the matching equation associated with interconnection and damping assignment passivity-based control designs (IDA-PBC). The stability of the controlled system is proved using the closed loop Hamiltonian as a Lyapunov candidate function. The performance of the proposed controller is shown in simulation.

Second-order elastic finite element analysis of structures using a single element per member

Finite element frame analysis programs targeted for design office application necessitate algorithms which can deliver reliable numerical convergence in a practical timeframe with comparable degrees of accuracy, and a highly desirable attribute is the use of a single element per member to reduce computational storage, as well as data preparation and the interpretation of the results. To this end, a higher-order finite element method including geometric non-linearity is addressed in the paper for the analysis of elastic frames for which a single element is used to model each member. The geometric non-linearity in the structure is handled using an updated Lagrangian formulation, which takes the effects of the large translations and rotations that occur at the joints into consideration by accumulating their nodal coordinates. Rigid body movements are eliminated from the local member load-displacement relationship for which the total secant stiffness is formulated for evaluating the large member deformations of an element. The influences of the axial force on the member stiffness and the changes in the member chord length are taken into account using a modified bowing function which is formulated in the total secant stiffness relationship, for which the coupling of the axial strain and flexural bowing is included.

A framework for testing robust autonomy of UAS during design and certification

As the number of Uninhabited Airborne Systems (UAS) proliferates in civil applications, industry is increasingly putting pressure on regulation authorities to provide a path for certification and allow UAS integration into regulated airspace. The success of this integration depends on developments in improved UAS reliability and safety, regulations for certification, and technologies for operational performance and safety assessment. This paper focusses on the last topic and describes a framework for quantifying robust autonomy of UAS, which quantifies the system's ability to either continue operating in the presence of faults or safely shut down. Two figures of merit are used to evaluate vehicle performance relative to mission requirements and the consequences of autonomous decision making in motion control and guidance systems. These figures of merit are interpreted within a probabilistic framework, which extends previous work in the literature. The valuation of the figures of merit can be done using stochastic simulation scenarios during both vehicle development and certification stages with different degrees of integration of hardware-in-the-loop simulation technology. The objective of the proposed framework is to aid in decision making about the suitability of a vehicle with respect to safety and reliability relative to mission requirements.

Conversion of linear to rhombic C-4 in the gas phase: A joint experimental and theoretical study

Charge reversal (CR) and neutralization reionization (NR) experiments carried out on a 4-sector mass spectrometer demonstrate that isotopically labeled, linear C-4 anion rearranges upon collisional oxidation. The cations and neutrals formed in these experiments exhibit differing degrees of isotopic scrambling in their fragmentation patterns, indicative of (at least) partial isomerization of both states. Theoretical studies, employing the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31G(d) level of theory, favor conversion to the rhombic C-4 isomer on both cationic and neutral potential-energy surfaces with the rhombic structures predicted to be slightly more stable than the linear forms in each case. The combination of experiment with theory indicates that the elusive rhombic C-4 is formed as a cation and as a neutral following charge stripping of linear C-4(-)