Structural identification of hindered amine light stabilisers in coil coatings using electrospray ionisation tandem mass spectrometry

Hindered amine light stabilisers (HALS) are the most effective antioxidants currently available for polymer systems in post-production, in-service applications, yet the mechanism of their action is still not fully understood. Structural characterisation of HALS in polymer matrices, particularly the identification of structural modifications brought about by oxidative conditions, is critical to aid mechanistic understanding of the prophylactic effects of these molecules. In this work, electrospray ionisation tandem mass spectrometry (ESI-MS/MS) was applied to the analysis of a suite of commercially available 2,2,6,6-tetramethylpiperidine-based HALS. Fragmentation mechanisms for the \[M + H](+) ions are proposed, which provide a rationale for the product ions observed in the MS/MS and MS(3) mass spectra of N-H, N-CH(3), N-C(O)CH(3) and N-OR containing HALS (where R is an alkyl substituent). A common product ion at m/z 123 was identified for the group of antioxidants containing N-H, N-CH3 or N-C(0)CH3 functionality, and this product ion was employed in precursor ion scans on a triple quadrupole mass spectrometer to identify the HALS species present in a crude extract from of a polyester-based coil coating. Using MS/MS, two degradation products were unambiguously identified. This technique provides a simple and selective approach to monitoring HALS structures within complex matrices. Copyright (C) 2010 John Wiley & Sons, Ltd.

Minimization of bauxite residue neutralization products using nanofiltered seawater

Currently, open circuit Bayer refineries pump seawater directly into their operations to neutralize the caustic fraction of the Bayer residue. The resulting supernatant has a reduced pH and is pumped back to the marine environment. This investigation has assessed modified seawater sources generated from nanofiltration processes to compare their relative capacities to neutralize bauxite residues. An assessment of the chemical stability of the neutralization products, neutralization efficiency, discharge water quality, bauxite residue composition, and associated economic benefits have been considered to determine the most preferable seawater filtration process based on implementation costs, savings to operations and environmental benefits. The mechanism of neutralization for each technology was determined to be predominately due to the formation of Bayer hydrotalcite and calcium carbonate, however variations in neutralization capacity and efficiencies have been observed. The neutralization efficiency of each feed source has been found to be dependent on the concentration of magnesium, aluminium, calcium and carbonate. Nanofiltered seawater with approximately double the amount of magnesium and calcium required half the volume of seawater to achieve the same degree of neutralization. These studies have revealed that multiple neutralization steps occur throughout the process using characterization techniques such as X-ray diffraction (XRD), infrared (IR) spectroscopy and inductively coupled plasma optical emission spectroscopy (ICP-OES).

Hip and knee kinematics display complex and time-varying sagittal kinematics during repetitive stepping: Implications for design of a functional fatigue model of the knee extensors and flexors

The validity of fatigue protocols involving multi-joint movements, such as stepping, has yet to be clearly defined. Although surface electromyography can monitor the fatigue state of individual muscles, the effects of joint angle and velocity variation on signal parameters are well established. Therefore, the aims of this study were to i) describe sagittal hip and knee kinematics during repetitive stepping ii) identify periods of high inter-trial variability and iii) determine within-test reliability of hip and knee kinematic profiles. A group of healthy men (N = 15) ascended and descended from a knee-high platform wearing a weighted vest (10%BW) for 50 consecutive trials. The hip and knee underwent rapid flexion and extension during step ascent and descent. Variability of hip and knee velocity peaked between 20-40% of the ascent phase and 80-100% of the descent. Significant (p<0.05) reductions in joint range of motion and peak velocity during step ascent were observed, while peak flexion velocity increased during descent. Healthy individuals use complex hip and knee motion to negotiate a knee-high step with kinematic patterns varying across multiple repetitions. These findings have important implications for future studies intending to use repetitive stepping as a fatigue model for the knee extensors and flexors.

Secreted products and extracellular matrix from testicular peritubular myoid cells influence androgen-binding protein secretion by Sertoli cells in culture

Metabolic cooperation mediated by secreted factors between Sertoli cells and peritubular myoid cells has been well documented. We have confirmed that factors secreted by peritubular myoid cells modulate androgen-binding protein (ABP) secretion by Sertoli cells and shown further that this can also be achieved with peritubular myoid cell extracellular matrix (ECM). While peritubular myoid cell ECM potentiated the stimulatory effect of dibutyryl cyclic AMP on Sertoli cell ABP secretion, secreted factors did not, suggesting that the two components influence Sertoli cells through distinct mechanisms. We also tested other factors and other cell lines for effects on ABP production by Sertoli cells. The addition of human plasma fibronectin or conditioned medium from the basement membrane-producing Englebreth-Holm- Swarm sarcoma also stimulated ABP secretion by Sertoli cells. Cocultures of epithelial Sertoli cells with the cells of mesenchymal origin, such as testicular peritubular myoid cells, embryonic skin fibroblasts, and bladder smooth muscle cells, significantly stimulated ABP secretion by Sertoli cells, but co-culture with the epithelial-derived Martin-Darby canine kidney cell line had no effect on Sertoli cell-secreted ABP levels. Our data further define the epithelial-mesenchymal cell interaction that exists between Sertoli cells and peritubular myoid cells in the mammalian testis.

The QUT innovation space : a trans-disciplinary learning environment for entrepreneurship education : final report

In the current climate of global economic volatility, there are increasing calls for training in enterprising skills and entrepreneurship to underpin the systemic innovation required for even medium-term business sustainability. The skills long-recognised as the essential for entrepreneurship now appear on the list of employability skills demanded by industry. The QUT Innovation Space (QIS) was an experiment aimed at delivering entrepreneurship education (EE), as an extra-curricular platform across the university, to the undergraduate students of an Australian higher education institute. It was an ambitious project that built on overseas models of EE studied during an Australian Learning and Teaching Council (ALTC) Teaching Fellowship (Collet, 2011) and implemented those approaches across an institute. Such EE approaches have not been attempted in an Australian university. The project tested resonance not only with the student population, from the perspective of what worked and what didn’t work, but also with every level of university operations. Such information is needed to inform the development of EE in the Australian university landscape. The QIS comprised a physical co-working space, virtual sites (web, Twitter and Facebook) and a network of entrepreneurial mentors, colleagues, and students. All facets of the QIS enabled connection between like-minded individuals that underpins the momentum needed for a project of this nature. The QIS became an innovation community within QUT. This report serves two purposes. First, as an account of the QIS project and its evolution, the report serves to identify the student demand for skills and training as well as barriers and facilitators of the activities that promote EE in an Australian university context. Second, the report serves as a how-to manual, in the tradition of many tomes on EE, outlining the QIS activities that worked as well as those that failed. The activities represent one measure of QIS outcomes and are described herein to facilitate implementation in other institutes. The QIS initially aimed to adopt an incubation model for training in EE. The ‘learning by doing’ model for new venture creation is a highly successful and high profile training approach commonly found in overseas contexts. However, the greatest demand of the QUT student population was not for incubation and progression of a developed entrepreneurial intent, but rather for training that instilled enterprising skills in the individual. These two scenarios require different training approaches (Fayolle and Gailly, 2008). The activities of the QIS evolved to meet that student demand. In addressing enterprising skills, the QIS developed the antecedents of entrepreneurialism (i.e., entrepreneurial attitudes, motivation and behaviours) including high-level skills around risk-taking, effective communication, opportunity recognition and action-orientation. In focusing on the would-be entrepreneur and not on the (initial) idea per se, the QIS also fostered entrepreneurial outcomes that would never have gained entry to the rigid stage-gated incubation model proposed for the original QIS framework. Important lessons learned from the project for development of an innovation community include the need to: 1. Evaluate the context of the type of EE program to be delivered and the student demand for the skills training (as noted above). 2. Create a community that builds on three dimensions: a physical space, a virtual environment and a network of mentors and partners. 3. Supplement the community with external partnerships that aid in delivery of skills training materials. 4. Ensure discovery of the community through the use of external IT services to deliver advertising and networking outlets. 5. Manage unrealistic student expectations of billion dollar products. 6. Continuously renew and rebuild simple activities to maintain student engagement. 7. Accommodate the non-university end-user group within the community. 8. Recognise and address the skills bottlenecks that serve as barriers to concept progression; in this case, externally provided IT and programming skills. 9. Use available on-line and published resources rather than engage in constructing project-specific resources that quickly become obsolete. 10. Avoid perceptions of faculty ownership and operate in an increasingly competitive environment. 11. Recognise that the continuum between creativity/innovation and entrepreneurship is complex, non-linear and requires different training regimes during the different phases of the pipeline. One small entity, such as the QIS, cannot address them all. The QIS successfully designed, implemented and delivered activities that included events, workshops, seminars and services to QUT students in the extra-curricular space. That the QIS project can be considered successful derives directly from the outcomes. First, the QIS project changed the lives of emerging QUT student entrepreneurs. Also, the QIS activities developed enterprising skills in students who did not necessarily have a business proposition, at the time. Second, successful outcomes of the QIS project are evidenced as the embedding of most, perhaps all, of the QIS activities in a new Chancellery-sponsored initiative: the Leadership Development and Innovation Program hosted by QUT Student Support Services. During the course of the QIS project, the Brisbane-based innovation ecosystem underwent substantial change. From a dearth of opportunities for the entrepreneurially inclined, there is now a plethora of entities that cater for a diversity of innovation-related activities. While the QIS evolved with the landscape, the demand endpoint of the QIS activities still highlights a gap in the local and national innovation ecosystems. The freedom to experiment and to fail is not catered for by the many new entities seeking to build viable businesses on the back of the innovation push. The onus of teaching the enterprising skills, which are the employability skills now demanded by industry, remains the domain of the higher education sector.

Proteins, drug targets and the mechanisms they control : the simple truth about complex networks

Realizing the promise of molecularly targeted inhibitors for cancer therapy will require a new level of knowledge about how a drug target is wired into the control circuitry of a complex cellular network. Here we review general homeostatic principles of cellular networks that enable the cell to be resilient in the face of molecular perturbations, while at the same time being sensitive to subtle input signals. Insights into such mechanisms may facilitate the development of combination therapies that take advantage of the cellular control circuitry, with the aim of achieving higher efficacy at a lower drug dosage and with a reduced probability of drug-resistance development.

Behavior of the electron temperature in nonuniform complex plasmas

The response of complex ionized gas systems to the presence of nonuniform distribution of charged grains is investigated using a kinetic model. Contrary to an existing view that the electron temperature inevitably increases in the grain-occupied region because of enhanced ionization to compensate for the electrons lost to the grains, it is shown that this happens only when the ionizing electric field increases in the electron depleted region. The results for two typical plasma systems suggest that when the ionizing electric field depends on the spatially averaged electron density, the electron temperature in the grain containing region can actually decrease.

Spatially averaged model of complex-plasma discharge with self-consistent electron energy distribution

A global, or averaged, model for complex low-pressure argon discharge plasmas containing dust grains is presented. The model consists of particle and power balance equations taking into account power loss on the dust grains and the discharge wall. The electron energy distribution is determined by a Boltzmann equation. The effects of the dust and the external conditions, such as the input power and neutral gas pressure, on the electron energy distribution, the electron temperature, the electron and ion number densities, and the dust charge are investigated. It is found that the dust subsystem can strongly affect the stationary state of the discharge by dynamically modifying the electron energy distribution, the electron temperature, the creation and loss of the plasma particles, as well as the power deposition. In particular, the power loss to the dust grains can take up a significant portion of the input power, often even exceeding the loss to the wall.

Low-pressure diffusion equilibrium of electronegative complex plasmas

A model for electronegative plasmas containing charged dust or colloidal grains was used. Numerical solutions based on the model demonstrate how a low-pressure diffusion equilibrium of the complex electronegative plasma system is dynamically sustained through plasma particle sources.

Ion-acoustic waves in a complex plasma with negative ions

A wave propagation in a complex dusty plasma with negative ions was considered. The relevant processes such as ionization, electron attachment, diffusion, positive-negative ion recombination, plasma particle collisions, as well as elastic Coulomb and inelastic dust-charging collisions were taken self-consistently. It was found that the equilibrium of the plasma as well as the propagation of ion waves were modified to various degrees by these effects.

Tailoring of ion species composition in complex plasmas with charge exchange collisions

A generic approach towards tailoring of ion species composition in reactive plasmas used for nanofabrication of various functional nanofilms and nanoassemblies, based on a simplified model of a parallel-plate rf discharge, is proposed. The model includes an idealized reactive plasma containing two neutral and two ionic species interacting via charge exchange collisions in the presence of a microdispersed solid component. It is shown that the number densities of the desired ionic species can be efficiently managed by adjusting the dilution of the working gas in a buffer gas, rates of electron impact ionization, losses of plasma species on the discharge walls, and surfaces of fine particles, charge exchange rates, and efficiency of three-body recombination processes in the plasma bulk. The results are relevant to the plasma-aided nanomanufacturing of ordered patterns of carbon nanotip and nanopyramid microemitters.

Electron energy distribution function in low-pressure complex plasmas

The effect of density and size of dust grains on the electron energy distribution function (EEDF) in low-temperature complex plasmas is studied. It is found that the EEDF depends strongly on the dust density and size. The behavior of the electron temperature can differ significantly from that of a pristine plasma. For low-pressure argon glow discharge, the Druyvesteyn-like EEDF often found in pristine plasmas can become nearly Maxwellian if the dust density and/or sizes are large. One can thus control the plasma parameters by the dust grains.

Modelling electronegative complex plasma systems

The control of the generation and assembly of the electronegative plasma-grown particles is discussed. Due to the large number of elementary processes of particle creation and loss, electronegative complex plasmas should be treated as open systems where the stationary states are sustained by various particle creation and loss processes in the plasma bulk, on the walls, and on the dust grain surfaces. To be physically self-consistent, ionization, diffusion, electron attachment, recombination, dust charge variation, and dissipation due to electron and ion elastic collisions with neutrals and fine particles, as well as charging collisions with the dust, must be accounted for.

Ion-acoustic waves in a complex plasma with negative ions

Negative ions and negatively charged micro- to nano-meter sized dust grains are ubiquitous in astrophysical as well as industrial processing plasmas. The negative ions can appear in electro-negative plasmas as a result of elementary processes such as dissociative or non-dissociative electron attachment to neutrals. They are usually rather small in number, and in general do not affect the overall plasma behavior. On the other hand, since the dust grains are almost always highly negative, even in small numbers they can take up a considerable proportion of the total negative charge in the system. The presence of dusts can affect the characteristics of most collective processes of the plasma since the charge balance in both the steady and dynamic states can be significantly altered. Another situation that often occurs is that the electron number density becomes small because of their absorption by the dust grains or the discharge walls. In this case the negative ions in the plasma can play a very important role. Here, a self-consistent theory of linear waves in complex laboratory plasmas containing dust grains and negative ions is presented. A comprehensive model for such plasmas including source and sink effects associated with the presence of dust grains and negative ions is introduced. The stationary state of the plasma as well as the dispersion and damping characteristics of the waves are investigated. All relevant processes, such as ionization, diffusion, electron attachment, negative-positive ion recombination, dust charge relaxation, and dissipation due to electron and ion elastic collisions with neutrals and dust particles, as well as charging collisions with the dusts, are taken into consideration.

Dynamic self-organization phenomena in complex ionized gas systems : new paradigms and technological aspects

An overview of dynamic self-organization phenomena in complex ionized gas systems, associated physical phenomena, and industrial applications is presented. The most recent experimental, theoretical, and modeling efforts to understand the growth mechanisms and dynamics of nano- and micron-sized particles, as well as the unique properties of the plasma-particle systems (colloidal, or complex plasmas) and the associated physical phenomena are reviewed and the major technological applications of micro- and nanoparticles are discussed. Until recently, such particles were considered mostly as a potential hazard for the microelectronic manufacturing and significant efforts were applied to remove them from the processing volume or suppress the gas-phase coagulation. Nowadays, fine clusters and particulates find numerous challenging applications in fundamental science as well as in nanotechnology and other leading high-tech industries.