Azo-linked corner porphyrin systems: synthesis, crystal structures and spectroscopic investigation

1,2-Bis[10,15-di(3,5-di-tert-butyl)phenylporphyrinatonickel(II)-5-yl]diazene was synthesised via copper catalysed coupling of aminated nickel(II) 5,10-diarylporphyrin (“corner porphyrin”) and its X-ray crystal structure was determined. Two different crystals yielded different structures, one with the free meso positions in a trans-like orientation, and the other with a cis-like disposition. The free meso positions of the obtained dimer have been further functionalised while the synthesis of a zinc analogue has so far been unsuccessful. The X-ray crystal structure of the dinitro derivative of the dinickel(II) azoporphyrin was determined, and the structure showed a cis-like disposition of the nitro groups.

Corner and finger formation in Hele-Shaw flow with kinetic undercooling regularisation

We examine the effect of a kinetic undercooling condition on the evolution of a free boundary in Hele--Shaw flow, in both bubble and channel geometries. We present analytical and numerical evidence that the bubble boundary is unstable and may develop one or more corners in finite time, for both expansion and contraction cases. This loss of regularity is interesting because it occurs regardless of whether the less viscous fluid is displacing the more viscous fluid, or vice versa. We show that small contracting bubbles are described to leading order by a well-studied geometric flow rule. Exact solutions to this asymptotic problem continue past the corner formation until the bubble contracts to a point as a slit in the limit. Lastly, we consider the evolving boundary with kinetic undercooling in a Saffman--Taylor channel geometry. The boundary may either form corners in finite time, or evolve to a single long finger travelling at constant speed, depending on the strength of kinetic undercooling. We demonstrate these two different behaviours numerically. For the travelling finger, we present results of a numerical solution method similar to that used to demonstrate the selection of discrete fingers by surface tension. With kinetic undercooling, a continuum of corner-free travelling fingers exists for any finger width above a critical value, which goes to zero as the kinetic undercooling vanishes. We have not been able to compute the discrete family of analytic solutions, predicted by previous asymptotic analysis, because the numerical scheme cannot distinguish between solutions characterised by analytic fingers and those which are corner-free but non-analytic.

Corner detection in images under different noise levels

Corner detection has shown its great importance in many computer vision tasks. However, in real-world applications, noise in the image strongly affects the performance of corner detectors. Few corner detectors have been designed to be robust to heavy noise by now, partly because the noise could be reduced by a denoising procedure. In this paper, we present a corner detector that could find discriminative corners in images contaminated by noise of different levels, without any denoising procedure. Candidate corners (i.e., features) are firstly detected by a modified SUSAN approach, and then false corners in noise are rejected based on their local characteristics. Features in flat regions are removed based on their intensity centroid, and features on edge structures are removed using the Harris response. The detector is self-adaptive to noise since the image signal-to-noise ratio (SNR) is automatically estimated to choose an appropriate threshold for refining features. Experimental results show that our detector has better performance at locating discriminative corners in images with strong noise than other widely used corner or keypoint detectors.

Peripheral higher order aberrations in emmetropes and myopes

Purpose: Poor image quality in the peripheral field may lead to myopia. Most studies measuring the higher order aberrations in the periphery have been restricted to the horizontal visual field. The purpose of this study was to measure higher order monochromatic aberrations across the central 42º horizontal x 32º vertical visual fields in myopes and emmetropes. ---------- Methods: We recruited 5 young emmetropes with spherical equivalent refractions +0.17 ± 0.45D and 5 young myopes with spherical equivalent refractions -3.9 ± 2.09D. Measurements were taken with a modified COAS-HD Hartmann-Shack aberrometer (Wavefront Sciences Inc). Measurements were taken while the subjects looked at 38 points arranged in a 7 x 6 matrix (excluding four corner points) through a beam splitter held between the instrument and the eye. A combination of the instrument’s software and our own software was used to estimate OSA Zernike coefficients for 5mm pupil diameter at 555nm for each point. The software took into account the elliptical shape of the off-axis pupil. Nasal and superior fields were taken to have positive x and y signs, respectively. ---------- Results: The total higher order RMS (HORMS) was similar on-axis for emmetropes (0.16 ± 0.02 μm) and myopes (0.17 ± 0.02 μm). There was no common pattern for HORMS for emmetropes across the visual field where as 4 out of 5 myopes showed a linear increase in HORMS in all directions away from the minimum. For all subjects, vertical and horizontal comas showed linear changes across the visual field. The mean rate of change of vertical coma across the vertical meridian was significantly lower (p = 0.008) for emmetropes (-0.005 ± 0.002 μm/deg) than for myopes (-0.013 ± 0.004 μm/deg). The mean rate of change of horizontal coma across the horizontal meridian was lower (p = 0.07) for emmetropes (-0.006 ± 0.003 μm/deg) than myopes (-0.011 ± 0.004 μm/deg). ---------- Conclusion: We have found differences in patterns of higher order aberrations across the visual fields of emmetropes and myopes, with myopes showing the greater rates of change of horizontal and vertical coma.

Chemical functionalities of high and low sulfur Australian coals : a case study using micro attenuated total reflectance–fourier transform infrared (ATR–FTIR) spectrometry

The macerals in bituminous coals with varying organic sulfur content from the Early Permian Greta Coal Measures at three locations (Southland Colliery, Drayton Colliery and the Cranky Corner Basin), in and around the Sydney Basin (Australia), have been studied using light-element electron microprobe (EMP) analysis and micro-ATR–FTIR. Electron microprobe analysis of individual macerals reveals that the vitrinite in both the Cranky Corner Basin and Drayton Colliery (Puxtrees seam) samples have similar carbon contents (ca. 78% C in telocollinite), suggesting that they are of equivalent rank. However, the Cranky Corner coals have anomalously low vitrinite reflectance (down to 0.45%) vs. the Drayton materials (ca. 0.7%). They also have very high organic S content (3–6.5%) and lower O content (ca. 10%) than the equivalent macerals in the Drayton sample (0.7% S and 15.6% O). A study was carried out to investigate the impacts of the high organic S on the functional groups of the macerals in these two otherwise iso-rank, stratigraphically-equivalent seams. An iso-rank low-S coal from the overlying Wittingham Coal Measures near Muswellbrook and coals of slightly higher rank from the Greta Coal Measures at Southland Colliery near Cessnock were also evaluated using the same techniques to extend the data set. Although the telocollinite in the Drayton and Cranky Corner coals have very similar carbon content (ca.78% C), the ATR–FTIR spectra of the vitrinite and inertinite macerals in these respectively low S and high S coals show some distinct differences in IR absorbance from various aliphatic and aromatic functional groups. The differences in absorbance of the aliphatic stretching bands (2800–3000 cm−1) and the aromatic carbon (CC) peak at 1606 cm−1 are very obvious. Compared to that of the Drayton sample (0.7% S and 15% O), the telocollinite of the Cranky Corner coal (6% S and 10% O) clearly shows: (i) less absorbance from OH groups, represented by a broad region around 3553 cm−1, (ii) much stronger aliphatic C–H absorbance (stretching modes around 3000–2800 cm−1 and bending modes around 1442 cm−1) and (iii) less absorbance from aromatic carbon functional groups (peaking at 1606 cm−1). Evaluation of the iso-rank Drayton and Cranky Corner coals shows that: (i) the aliphatic C–H absorbances decrease with increasing oxygen content but increase with increasing organic S content and (ii) the aromatic H to aliphatic H ratio (Har/Hali) for the telocollinite increases with (organic) O%, but decreases progressively with increasing organic S. The high organic S content in the maceral appears to be accompanied by a greater proportion of aliphatic functional groups, possibly as a result of some of the O within maceral ring structures in the high S coal samples being replaced.

Azo- and butadiyne-linked 5,10-diarylporphyrins

Porphyrins are one of Nature’s essential building blocks that play an important role in several biological systems including oxygen transport, photosynthesis, and enzymes. Their capacity to absorb visible light, facilitate oxidation and reduction, and act as energy- and electron-transfer agents, in particular when several are held closely together, is of interest to chemists who seek to mimic Nature and to make and use these compounds in order to synthesise novel advanced materials. During this project 26 new 5,10-diarylsubstituted porphyrin monomers, 10 dimers, and 1 tetramer were synthesised. The spectroscopic and structural properties of these compounds were investigated using 1D/2D 1H NMR, UV/visible, ATR-IR and Raman spectroscopy, mass spectrometry, X-ray crystallography, electrochemistry and gel permeation chromatography. Nitration, amination, bromination and alkynylation of only one as well as both of the meso positions of the porphyrin monomers have resulted in the expansion of the synthetic possibilities for the 5,10-diarylsubstituted porphyrins. The development of these new porphyrin monomers has led to the successful synthesis of new azo- and butadiyne-linked dimers. The functionalisation of these compounds was investigated, in particular nitration, amination, and bromination. The synthesised dimers containing the azo bridge have absorption spectra that show a large split in the Soret bands and intense Q-bands that have been significantly redshifted. The butadiyne dimers also have intense, red-shifted Q-bands but smaller Soret band splittings. Crystal structures of two new azoporphyrins have been acquired and compared to the azoporphyrin previously synthesised from 5,10,15- triarylsubstituted porphyrin monomers. A completely new cyclic porphyrin oligomer (CPO) was synthesised comprising four porphyrin monomers linked by azo and butadiyne bridges. This is the first cyclic tetramer that has both the azo and butadiyne linking groups. The absorption spectrum of the tetramer exhibits a large Soret split making it more similar to the azo- dimers than the butadiyne-linked dimers. The spectroscopic characteristics of the synthesised tetramer have been compared to the characteristics of other cyclic porphyrin tetramers. The collected data indicate that the new synthesised cyclic tetramer has a more efficient ð-overlap and a better ground state electronic communication between the porphyrin rings.

On democracy

If one clear argument emerged from my doctoral thesis in political science, it is that there is no agreement as to what democracy is. There are over 40 different varieties of democracy ranging from those in the mainstream with subtle or minute differences to those playing by themselves in the corner. And many of these various types of democracy are very well argued, empirically supported, and highly relevant to certain polities. The irony is that the thing which all of these democratic varieties or the ‘basic democracy’ that all other forms of democracy stem from, is elusive. There is no international agreement in the literature or in political practice as to what ‘basic democracy’ is and that is problematic as many of us use the word ‘democracy’ every day and it is a concept of tremendous importance internationally. I am still uncertain as to why this problem has not been resolved before by far greater minds than my own, and it may have something to do with the recent growth in democratic theory this past decade and the innovative areas of thought my thesis required, but I think I’ve got the answer. By listing each type of democracy and filling the column next to this list with the literature associated with these various styles of democracy, I amassed a large and comprehensive body of textual data. My research intended to find out what these various styles of democracy had in common and to create a taxonomy (like the ‘tree of life’ in biology) of democracy to attempt at showing how various styles of democracy have ‘evolved’ over the past 5000 years.ii I then ran a word frequency analysis program or a piece of software that counts the 100 most commonly used words in the texts. This is where my logic came in as I had to make sense of these words. How did they answer what the most fundamental commonalities are between 40 different styles of democracy? I used a grounded theory analysis which required that I argue my way through these words to form a ‘theory’ or plausible explanation as to why these particular words and not others are the important ones for answering the question. It came down to the argument that all 40 styles of democracy analysed have the following in common 1) A concept of a citizenry. 2) A concept of sovereignty. 3) A concept of equality. 4) A concept of law. 5) A concept of communication. 6) And a concept of selecting officials. Thus, democracy is a defined citizenry with its own concept of sovereignty which it exercises through the institutions which support the citizenry’s understandings of equality, law, communication, and the selection of officials. Once any of these 6 concepts are defined in a particular way it creates a style of democracy. From this, we can also see that there can be more than one style of democracy active in a particular government as a citizenry is composed of many different aggregates with their own understandings of the six concepts.

Multiple camera management using wide baseline matching

Camera calibration information is required in order for multiple camera networks to deliver more than the sum of many single camera systems. Methods exist for manually calibrating cameras with high accuracy. Manually calibrating networks with many cameras is, however, time consuming, expensive and impractical for networks that undergo frequent change. For this reason, automatic calibration techniques have been vigorously researched in recent years. Fully automatic calibration methods depend on the ability to automatically find point correspondences between overlapping views. In typical camera networks, cameras are placed far apart to maximise coverage. This is referred to as a wide base-line scenario. Finding sufficient correspondences for camera calibration in wide base-line scenarios presents a significant challenge. This thesis focuses on developing more effective and efficient techniques for finding correspondences in uncalibrated, wide baseline, multiple-camera scenarios. The project consists of two major areas of work. The first is the development of more effective and efficient view covariant local feature extractors. The second area involves finding methods to extract scene information using the information contained in a limited set of matched affine features. Several novel affine adaptation techniques for salient features have been developed. A method is presented for efficiently computing the discrete scale space primal sketch of local image features. A scale selection method was implemented that makes use of the primal sketch. The primal sketch-based scale selection method has several advantages over the existing methods. It allows greater freedom in how the scale space is sampled, enables more accurate scale selection, is more effective at combining different functions for spatial position and scale selection, and leads to greater computational efficiency. Existing affine adaptation methods make use of the second moment matrix to estimate the local affine shape of local image features. In this thesis, it is shown that the Hessian matrix can be used in a similar way to estimate local feature shape. The Hessian matrix is effective for estimating the shape of blob-like structures, but is less effective for corner structures. It is simpler to compute than the second moment matrix, leading to a significant reduction in computational cost. A wide baseline dense correspondence extraction system, called WiDense, is presented in this thesis. It allows the extraction of large numbers of additional accurate correspondences, given only a few initial putative correspondences. It consists of the following algorithms: An affine region alignment algorithm that ensures accurate alignment between matched features; A method for extracting more matches in the vicinity of a matched pair of affine features, using the alignment information contained in the match; An algorithm for extracting large numbers of highly accurate point correspondences from an aligned pair of feature regions. Experiments show that the correspondences generated by the WiDense system improves the success rate of computing the epipolar geometry of very widely separated views. This new method is successful in many cases where the features produced by the best wide baseline matching algorithms are insufficient for computing the scene geometry.

Smoothly attaching bow flows with constant vorticity

The free surface flow of a finite depth fluid past a semi-infinite body is considered. The fluid is assumed to have constant vorticity throughout and the free surface is assumed to attach smoothly to the front face of the body. Numerical solutions are found using a boundary integral method in the physical plane and it is shown that solutions exist for all supercritical Froude numbers. The related problem of the cusp-like flow due to a submerged sink in a corner is also considered. Vorticity is included in the flow and it is shown that the behaviour of the solutions is qualitatively the same as that found in the problem described above.

Response : letter to the editor by Al-Azri and Al-Maniri

Firstly, the authors would like to thank the editor for the opportunity to respond to Dr Al-Azri’s and Dr Al-Maniri’s letter. Secondly, while the current authors also accept that deterrence-based approaches should act as only one corner-stone of a suite of interventions and public policy initiatives designed to improve road safety, deterrence-based approaches have nonetheless consistently proven to be a valuable resource to improve road safety. Dr Al-Azri and Dr Al-Maniri reinforce their assertion about the limited utility of deterrence by citing drink driving research, and the issue of drink driving is particularly relevant within the current context given that the problem of driving after drinking has historically been addressed through deterrence-based approaches. While the effectiveness of deterrence-based approaches to reduce drink driving will always be dependent upon a range of situational and contextual factors (including police enforcement practices, cultural norms, etc), the utilisation of this approach has proven particularly effective within Queensland, Australia. For example, a relatively recent comprehensive review of Random Breath Testing in Queensland demonstrated that this initiative not only had a deterrent impact upon self-reported intentions to drink and drive, but was also found to have significantly reduced alcohol-related fatalities in the state. However, the authors agree that deterrence-based approaches can be particularly transient and thus require constant “topping up” not least through sustained public reinforcement, which was clearly articulated in the seminal work by Homel.

Negative determinant of Hessian features

Local image feature extractors that select local maxima of the determinant of Hessian function have been shown to perform well and are widely used. This paper introduces the negative local minima of the determinant of Hessian function for local feature extraction. The properties and scale-space behaviour of these features are examined and found to be desirable for feature extraction. It is shown how this new feature type can be implemented along with the existing local maxima approach at negligible extra processing cost. Applications to affine covariant feature extraction and sub-pixel precise corner extraction are demonstrated. Experimental results indicate that the new corner detector is more robust to image blur and noise than existing methods. It is also accurate for a broader range of corner geometries. An affine covariant feature extractor is implemented by combining the minima of the determinant of Hessian with existing scale and shape adaptation methods. This extractor can be implemented along side the existing Hessian maxima extractor simply by finding both minima and maxima during the initial extraction stage. The minima features increase the number of correspondences by two to four fold. The additional minima features are very distinct from the maxima features in descriptor space and do not make the matching process more ambiguous.

Living City 2010 Workshop

Living City 2010 was a three-day place-based urban design immersion workshop program held at Logan Road Conference Centre, Stones Corner, for 30 self-selected Year 11 Visual Art Students and 4 Teachers drawn from 11 state and private Brisbane Secondary Schools, that focused on the active Brisbane City Council redevelopment site of Stones Corner, specifically Logan Road, public spaces at Stones Corner Library and rehabilitation of the nearby creek corridor. The workshop, framed within notions of ecological, economic, social and cultural sustainability, aimed to raise awareness of the layered complexity and perspectives involved in the design of shared city spaces and to encourage young people to voice their own concerns as future citizens about the shape and direction of their city. On Day 1, Brisbane City Council Public Art Officers Brendan Doherty and Genevieve Searle, local landscape architect Peter Boyle (Verge) and artists Malcolm Enright and Barbara Heath provided students with an overview of the historic and future context of the area including proposed design and public art interventions, followed by a site walk. The afternoon session, led by Natalie Wright and QUT design staff and students, focused on design tools to assist in the tackling of the redesign of the Stones Corner library precinct, where students worked on ideas. On Day 2, students were mentored by artist Liam Key to participate in a computer animation activity using the built environment as a canvas, and by artist Sebastian Moody to participate in an activity using red helium balloons as a playful catalyst for interaction to activate and create new public space. Later, students worked in teams on their ideas for redevelopment of the site in preparation for their Day 3 presentations. The workshop culminated in an exchange of planning ideas with Georgina Aitchison from Brisbane City Council's Urban Renewal Division. Students were introduced to design methodology, team thinking strategies, the scope of design practices and professions, presentation skills and post-secondary pathways, while participating teachers acquired content and design learning strategies transferable in many other contexts.

Effectiveness of powered hospital bed movers for reducing physiological strain and back muscle activation

Battery powered bed movers are becoming increasingly common within the hospital setting. The use of powered bed movers is believed to result in reduced physical efforts required by health care workers, which may be associated with a decreased risk of occupation related injuries. However, little work has been conducted assessing how powered bed movers impact on levels of physiological strain and muscle activation for the user. The muscular efforts associated with moving hospital beds using three different methods; manual pushing, StaminaLift Bed Mover (SBM) and Gzunda Bed Mover (GBM)were measured on six male subjects. Fourteen muscles were assessed moving a weighted hospital bed along a standardized route in an Australian hospital environment. Trunk inclination and upper spine acceleration were also quantified. Powered bed movers exhibited significantly lower muscle activation levels than manual pushing for the majority of muscles. When using the SBM, users adopted a more upright posture which was maintained while performing different tasks (e.g. turning a corner, entering a lift), while trunk inclination varied considerably for manual pushing and the GBM. The reduction in lower back muscular activation levels and the load reducing effect of a more upright posture may result in lower incidence of lower back injury.

A vibrational spectroscopic study of the phosphate mineral Wardite NaAl3(PO4)2(OH)4•2(H2O)

Three wardite mineral samples from different origins have been analysed by vibrational spectroscopy. The mineral is unusual in that it belongs to a unique symmetry class, namely the tetragonal-trapezohedral group. The structure of wardite contains layers of corner-linked –OH bridged MO6 octahedra stacked along the tetragonal C-axis in a four-layer sequence and linked by PO4 groups. Consequentially not all phosphate units are identical. Thus, two intense Raman bands observed at 995 and 1051 cm-1 are assigned to the ν1 PO43- symmetric stretching mode. Intense Raman bands are observed at 605 and 618 cm-1 with shoulders at 578 and 589 cm-1 are assigned to the ν4 out of plane bending modes of the PO43-. The observation of multiple bands supports the concept of non-equivalent phosphate units in the structure. Sharp infrared bands are observed at 3544 and 3611 cm-1 are attributed to the OH stretching vibrations of the hydroxyl units. Vibrational spectroscopy enables subtle details of the molecular structure of wardite to be determined.