Porphyrin containing isoindoline nitroxides as potential fluorescence sensors of free radicals

A series of new spin-labeled porphyrin containing isoindoline nitroxide moieties were synthesized and characterized as potential free radical fluorescence sensors. Fluorescence-suppression was observed in the free-base monoradical porphyrins, whilst the free-base biradical porphyrins exhibited highly suppressed fluorescence about three times greater than the monoradical porphyrins. The observed fluorescence-suppression was attributed to enhanced intersystem crossing resulting from electronexchange between the doublet nitroxide and the excited porphyrin fluorophore. Notably, fluorescencesuppression was not as strong in the related metalated porphyrins, possibly due to insufficient spin coupling between the nitroxide and the porphyrin. Continuous wave EPR spectroscopy of the diradical porphyrins in fluid solution suggests that the nitroxyl-nitroxyl interspin distance is long enough and tumbling is fast enough not to detect dipolar coupling.

Your voice counts : Listening to the voice of high school students with autism spectrum disorder

Supporting students with Autism Spectrum Disorders (ASD) in inclusive settings presents both opportunities and significant challenges to school communities. This study, which explored the lived-experience of nine students with ASD in an inclusive high school in Australia, is based on the belief that by listening to the voices of students, school communities will be in a better position to collaboratively create supportive learning and social environments. The findings of this small-scale study deepen our knowledge from the student perspective of the inclusive educational practices that facilitate and constrain the learning and participation of students with ASD. The students’ perspectives were examined in relation to the characteristics of successful inclusive schools identified by Kluth. Implications for inclusive educational practice that meets the needs of students with ASD are presented.

Two-Photon Fluorescence Microscopy Imaging of Cellular Oxidative Stress Using Profluorescent Nitroxides

A range of varying chromophore nitroxide free radicals and their nonradical methoxyamine analogues were synthesized and their linear photophysical properties examined. The presence of the proximate free radical masks the chromophore’s usual fluorescence emission, and these species are described as profluorescent. Two nitroxides incorporating anthracene and fluorescein chromophores (compounds 7 and 19, respectively) exhibited two-photon absorption (2PA) cross sections of approximately 400 G.M. when excited at wavelengths greater than 800 nm. Both of these profluorescent nitroxides demonstrated low cytotoxicity toward Chinese hamster ovary (CHO) cells. Imaging colocalization experiments with the commercially available CellROX Deep Red oxidative stress monitor demonstrated good cellular uptake of the nitroxide probes. Sensitivity of the nitroxide probes to H2O2-induced damage was also demonstrated by both one- and two-photon fluorescence microscopy. These profluorescent nitroxide probes are potentially powerful tools for imaging oxidative stress in biological systems, and they essentially “light up” in the presence of certain species generated from oxidative stress. The high ratio of the fluorescence quantum yield between the profluorescent nitroxide species and their nonradical adducts provides the sensitivity required for measuring a range of cellular redox environments. Furthermore, their reasonable 2PA cross sections provide for the option of using two-photon fluorescence microscopy, which circumvents commonly encountered disadvantages associated with one-photon imaging such as photobleaching and poor tissue penetration.

Homo- and heteronuclear meso,meso-(E)-Ethene-1,2-diyl-Linked Diporphyrins : preparation, X-ray crystal structure, electronic absorption and emission spectra and density functional theory calculations

Homo-and heteronuclear meso,meso-(E)-ethene-1,2-diyl-linked diporphyrins have been prepared by the Suzuki coupling of porphyrinylboronates and iodovinylporphyrins. Combinations comprising 5,10,15-triphenylporphyrin (TriPP) on both ends of the ethene-1,2-diyl bridge M 210 (M 2=H 2/Ni, Ni 2, Ni/Zn, H 4, H 2Zn, Zn 2) and 5,15-bis(3,5-di-tert-butylphenyl)porphyrinato-nickel(II) on one end and H 2, Ni, and ZnTriPP on the other (M 211), enable the first studies of this class of compounds possessing intrinsic polarity. The compounds were characterized by electronic absorption and steady state emission spectra, 1H NMR spectra, and for the Ni 2 bis(TriPP) complex Ni 210, single crystal X-ray structure determination. The crystal structure shows ruffled distortions of the porphyrin rings, typical of Ni II porphyrins, and the (E)-C 2H 2 bridge makes a dihedral angle of 50° with the mean planes of the macrocycles. The result is a stepped parallel arrangement of the porphyrin rings. The dihedral angles in the solid state reflect the interplay of steric and electronic effects of the bridge on interporphyrin communication. The emission spectra in particular, suggest energy transfer across the bridge is fast in conformations in which the bridge is nearly coplanar with the rings. Comparisons of the fluorescence behaviour of H 410 and H 2Ni10 show strong quenching of the free base fluorescence when the complex is excited at the lower energy component of the Soret band, a feature associated in the literature with more planar conformations. TDDFT calculations on the gas-phase optimized geometry of Ni 210 reproduce the features of the experimental electronic absorption spectrum within 0.1 eV. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectrum sensing using two-stage detection to compensate for reduced primary user duty cycle

Spectrum sensing is considered to be one of the most important tasks in cognitive radio. One of the common assumption among current spectrum sensing detectors is the full presence or complete absence of the primary user within the sensing period. In reality, there are many situations where the primary user signal only occupies a portion of the observed signal and the assumption of primary user duty cycle not necessarily fulfilled. In this paper we show that the true detection performance can degrade from the assumed achievable values when the observed primary user exhibits a certain duty cycle. Therefore, a two-stage detection method incorporating primary user duty cycle that enhances the detection performance is proposed. The proposed detector can improve the probability of detection under low duty cycle at the expense of a small decrease in performance at high duty cycle.

From slum to suburbia : examining a spectrum of planned and unplanned urban morphology in humid sub-tropical regions of the world

The current rapid urban growth throughout the world manifests in various ways and historically cities have grown, similarly, alternately or simultaneously between planned extensions and organic informal settlements (Mumford, 1989). Within cities different urban morphological regions can reveal different contexts of economic growth and/or periods of dramatic social/technological change (Whitehand, 2001, 105). Morpho-typological study of alternate contexts can present alternative models and contribute to the present discourse which questions traditional paradigms of urban planning and design (Todes et al, 2010). In this study a series of cities are examined as a preliminary exploration into the urban morphology of cities in ‘humid subtropical’ climates. From an initial set of twenty, six cities were selected: Sao Paulo, Brazil; Jacksonville, USA; Maputo, Mozambique; Kanpur, India; Hong Kong, China; and Brisbane, Australia. The urban form was analysed from satellite imagery at a constant scale. Urban morphological regions (types) were identified as those demonstrating particular consistant characteristics of form (density, typology and pattern) different to their surroundings when examined at a constant scale. This analysis was correlated against existing data and literature discussing the proliferation of two types of urban development, ‘informal settlement’ (defined here as self-organised communities identifiable but not always synonymous with ‘slums’) and ‘suburbia’ (defined here as master planned communities of generally detached houses prevalent in western society) - the extreme ends of a hypothetical spectrum from ‘planned’ to ‘spontaneous’ urban development. Preliminary results show some cities contain a wide variety of urban form ranging from the highly organic ‘self-organised’ type to the highly planned ‘master planned community’ (in the case of Sao Paulo) while others tend to fall at one end of the planning spectrum or the other (more planned in the cases of Brisbane and Jacksonville; and both highly planned and highly organic in the case of Maputo). Further research will examine the social, economical and political drivers and controls which lead to this diversity or homogeneity of urban form and speculates on the role of self-organisation as a process for the adaptation of urban form.

An analytical tool that quantifies cellular morphology changes from three-dimensional fluorescence images

The most common software analysis tools available for measuring fluorescence images are for two-dimensional (2D) data that rely on manual settings for inclusion and exclusion of data points, and computer-aided pattern recognition to support the interpretation and findings of the analysis. It has become increasingly important to be able to measure fluorescence images constructed from three-dimensional (3D) datasets in order to be able to capture the complexity of cellular dynamics and understand the basis of cellular plasticity within biological systems. Sophisticated microscopy instruments have permitted the visualization of 3D fluorescence images through the acquisition of multispectral fluorescence images and powerful analytical software that reconstructs the images from confocal stacks that then provide a 3D representation of the collected 2D images. Advanced design-based stereology methods have progressed from the approximation and assumptions of the original model-based stereology(1) even in complex tissue sections(2). Despite these scientific advances in microscopy, a need remains for an automated analytic method that fully exploits the intrinsic 3D data to allow for the analysis and quantification of the complex changes in cell morphology, protein localization and receptor trafficking. Current techniques available to quantify fluorescence images include Meta-Morph (Molecular Devices, Sunnyvale, CA) and Image J (NIH) which provide manual analysis. Imaris (Andor Technology, Belfast, Northern Ireland) software provides the feature MeasurementPro, which allows the manual creation of measurement points that can be placed in a volume image or drawn on a series of 2D slices to create a 3D object. This method is useful for single-click point measurements to measure a line distance between two objects or to create a polygon that encloses a region of interest, but it is difficult to apply to complex cellular network structures. Filament Tracer (Andor) allows automatic detection of the 3D neuronal filament-like however, this module has been developed to measure defined structures such as neurons, which are comprised of dendrites, axons and spines (tree-like structure). This module has been ingeniously utilized to make morphological measurements to non-neuronal cells(3), however, the output data provide information of an extended cellular network by using a software that depends on a defined cell shape rather than being an amorphous-shaped cellular model. To overcome the issue of analyzing amorphous-shaped cells and making the software more suitable to a biological application, Imaris developed Imaris Cell. This was a scientific project with the Eidgenössische Technische Hochschule, which has been developed to calculate the relationship between cells and organelles. While the software enables the detection of biological constraints, by forcing one nucleus per cell and using cell membranes to segment cells, it cannot be utilized to analyze fluorescence data that are not continuous because ideally it builds cell surface without void spaces. To our knowledge, at present no user-modifiable automated approach that provides morphometric information from 3D fluorescence images has been developed that achieves cellular spatial information of an undefined shape (Figure 1). We have developed an analytical platform using the Imaris core software module and Imaris XT interfaced to MATLAB (Mat Works, Inc.). These tools allow the 3D measurement of cells without a pre-defined shape and with inconsistent fluorescence network components. Furthermore, this method will allow researchers who have extended expertise in biological systems, but not familiarity to computer applications, to perform quantification of morphological changes in cell dynamics.

Spectrum sensing, detection and optimisation in cognitive radio for non-stationary primary user signals

Cognitive radio is an emerging technology proposing the concept of dynamic spec- trum access as a solution to the looming problem of spectrum scarcity caused by the growth in wireless communication systems. Under the proposed concept, non- licensed, secondary users (SU) can access spectrum owned by licensed, primary users (PU) so long as interference to PU are kept minimal. Spectrum sensing is a crucial task in cognitive radio whereby the SU senses the spectrum to detect the presence or absence of any PU signal. Conventional spectrum sensing assumes the PU signal as ‘stationary’ and remains in the same activity state during the sensing cycle, while an emerging trend models PU as ‘non-stationary’ and undergoes state changes. Existing studies have focused on non-stationary PU during the transmission period, however very little research considered the impact on spectrum sensing when the PU is non-stationary during the sensing period. The concept of PU duty cycle is developed as a tool to analyse the performance of spectrum sensing detectors when detecting non-stationary PU signals. New detectors are also proposed to optimise detection with respect to duty cycle ex- hibited by the PU. This research consists of two major investigations. The first stage investigates the impact of duty cycle on the performance of existing detec- tors and the extent of the problem in existing studies. The second stage develops new detection models and frameworks to ensure the integrity of spectrum sensing when detecting non-stationary PU signals. The first investigation demonstrates that conventional signal model formulated for stationary PU does not accurately reflect the behaviour of a non-stationary PU. Therefore the performance calculated and assumed to be achievable by the conventional detector does not reflect actual performance achieved. Through analysing the statistical properties of duty cycle, performance degradation is proved to be a problem that cannot be easily neglected in existing sensing studies when PU is modelled as non-stationary. The second investigation presents detectors that are aware of the duty cycle ex- hibited by a non-stationary PU. A two stage detection model is proposed to improve the detection performance and robustness to changes in duty cycle. This detector is most suitable for applications that require long sensing periods. A second detector, the duty cycle based energy detector is formulated by integrat- ing the distribution of duty cycle into the test statistic of the energy detector and suitable for short sensing periods. The decision threshold is optimised with respect to the traffic model of the PU, hence the proposed detector can calculate average detection performance that reflect realistic results. A detection framework for the application of spectrum sensing optimisation is proposed to provide clear guidance on the constraints on sensing and detection model. Following this framework will ensure the signal model accurately reflects practical behaviour while the detection model implemented is also suitable for the desired detection assumption. Based on this framework, a spectrum sensing optimisation algorithm is further developed to maximise the sensing efficiency for non-stationary PU. New optimisation constraints are derived to account for any PU state changes within the sensing cycle while implementing the proposed duty cycle based detector.

Children with autistic spectrum disorder have an associated risk of depression

Over recent years there has been an increase in the literature examining youth with Autism Spectrum Disorders (ASD). The growth in this area of research has highlighted a significant gap in our understanding of suitable interventions for people with ASD and the treatment of co-occurring psychiatric disorders.1-3 Children with ASD are at increased risk of experiencing depressive symptoms and developing depression; however with very few proven interventions available for preventing and treating depression in children with ASD, there is a need for further research in this area.

Spectrum sensing optimisation for dynamic primary user signal

We propose a multi-layer spectrum sensing optimisation algorithm to maximise sensing efficiency by computing the optimal sensing and transmission durations for a fast changing, dynamic primary user. Dynamic primary user traffic is modelled as a random process, where the primary user changes states during both the sensing period and transmission period to reflect a more realistic scenario. Furthermore, we formulate joint constraints to correctly reflect interference to the primary user and lost opportunity of the secondary user during the transmission period. Finally, we implement a novel duty cycle based detector that is optimised with respect to PU traffic to accurately detect primary user activity during the sensing period. Simulation results show that unlike currently used detection models, the proposed algorithm can jointly optimise the sensing and transmission durations to simultaneously satisfy the optimisation constraints for the considered primary user traffic.

Incongruence between self-reported and observed senior physical education teaching styles : an analysis using Mosston and Ashworth’s spectrum

Pedagogical styles, methods, models, practices or strategies are valued for what they claim they can achieve. In recent times curriculum documents and governments have called for a range of teaching approaches to meet the variety of learner differences and allow students to make more independent decision making in physical education (Hardy and Mawer, 1999). One well known system of categorizing teaching styles is the Mosston and Ashworth’s Spectrum of Teaching Styles (2002). In Queensland, prior to 2005, no research had been conducted on the teaching styles used by teachers of Physical Education. However, many teachers self-reported that they employed a variety of teaching styles depending on the aims and content of the material to be taught (Cothran, et al., 2005). This research, for the first time, collected teacher’s self-reported use of teaching styles and through observations verify the styles that were being used to teach Senior Physical Education in Queensland. More specifically the aims of the research were to determine: a) What teaching styles teachers of Senior Physical Education in Queensland believe they use? i) Were they using a range of teaching styles? ii) Were teachers of Senior Physical Education in Queensland using teaching styles that the Queensland Senior Physical Education Syllabus (2004) required? b) If Mosston and Ashworth’s (2002) Spectrum of Teaching Styles were used to categorise styles observed during the teaching of Senior Physical Education did the styles being used provide opportunities for evaluating as described by the Queensland Senior Physical Education Syllabus (2004)? The research was conducted in two phases. Part A involved use of a questionnaire to determine the teaching styles Queensland teachers of Senior Physical Education reported using and how often they reported using them. The questionnaire was administered to 110 teachers throughout Queensland. The sample was determined from 346 schools teaching Senior Physical Education (in 2006) across the state of Queensland, Australia. 286 questionnaires were sent to 77 non-randomised schools. There were 66 male and 44 female respondents in the sample. A wide range of teaching styles were reportedly used by teachers of Senior Physical Education with Practice Style-Style B, Command Style-Style A and Divergent Discovery Style-Style H, the most reportedly used. The Self-Teaching Style-Style K was reportedly used the least by teachers involved in this study. From the respondents a group of teachers were identified to form the participants for Part B. Part B of the study involved observation of a group of volunteer participants (from those who had completed the questionnaire) who displayed many of the ‘typical’ characteristics, and a cross-section of backgrounds, of teachers of Senior Physical Education in Queensland. In the case of this study, the criteria used to select the group of teachers to be observed teaching were, teaching experience (number of years: 0-4, 5-10 and 11 years and over), gender, geographical location of schools (focused on Brisbane and near area for travel/access purposes), profile of the students at schools (girls, boys or co-educational), nature of school (Government or Private) and the physical activities being taught in a school (activities to reflect all the areas of physical activity outlined within the syllabus). A total of 27 questionnaire respondents from Part A indicated that they were willing to be observed teaching practical lessons. The respondents who volunteered to be involved in Part B of the study came from different regions across the state of Queensland and was not confined to the Brisbane metropolitan area or large cities. From the group of people who volunteered for Part B four came from outside Brisbane and 23 from the Brisbane area. The final observation group of nine participants included eight teachers from the Brisbane area and one from a rural area. The characteristics of the final group included three females and six males from private and public schools with a range of teaching experience in years and a range of physical activities. Four year 12 and five year 11 teachers and their classes were videoed on three occasions as they progressed through an eight – nine week unit of work. This resulted in 24 hours 48 minutes and 20 seconds (or 4465 observations) of video teaching data which was subsequently coded by several researchers (99% interobserver reliability) to determine the teaching styles employed by the participants. This research indicated that, based on Mosston and Ashworth’s (2002) Spectrum of Teaching Styles, teachers of Senior Physical Education in Queensland used predominantly one style to teach 27 observed lessons. This is in sharp contrast to the variety of styles 110 teachers self- reportedly used and in spite of the Queensland Senior Physical Education Syllabus (2004) suggesting a range of specific styles be used. These results are discussed in the context of the Queensland Senior Physical Education Syllabus (2004), teacher knowledge of teaching styles and high-stakes curriculum and external pressures such as national testing and the publication of data from schools in tabloid newspapers. The data and findings in this research provide a rationale for improving teacher knowledge regarding teaching styles and the need for a clear definition of terminology in syllabus documents. Careful examination of the effects that the publishing of school data may have on teaching styles is advised. This research not only collected teacher’s perceptions of the teaching styles they believed they used it also verified these claims through direct observations of the teachers while teaching. These findings are relevant to syllabus writers, teacher educators, policy makers within education and teachers.