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.

One-dimensional hydrogen-bonded structures in the 1:1 proton-transfer salts of 4,5-dichlorophthalic acid with the aliphatic Lewis bases diisopropylamine and hexamethylenetetramine

The crystal structures of the 1:1 proton-transfer compounds of 4,5-dichlorophthalic acid with the aliphatic Lewis bases diisopropylamine and hexamethylenetetramine, viz. diisopropylaminium 2-carboxy-4,5-dichlorobenzoate (1) and hexamethylenetetraminium 2-carboxy-4,5-dichlorobenzoate hemihydrate (2), have been determined. Crystals of both 1 and 2 are triclinic, space group P-1, with Z = 2 in cells with a = 7.0299(5), b = 9.4712(7), c = 12.790(1)Å, α = 99.476(6), β = 100.843(6), γ = 97.578(6)o (1) and a = 7.5624(8), b = 9.8918(8), c = 11.5881(16)Å, α = 65.660(6), β = 86.583(4), γ = 86.987(8)o (2). In each, one-dimensional hydrogen-bonded chain structures are found: in 1 formed through aminium N+-H...Ocarboxyl cation-anion interactions. In 2, the chains are formed through anion carboxyl O...H-Obridging water interactions with the cations peripherally bound. In both structures, the hydrogen phthalate anions are essentially planar with short intra-species carboxylic acid O-H...Ocarboxyl hydrogen bonds [O…O, 2.381(3) Å (1) and 2.381(8) Å (2)].

Infrastructure sustainability : differential axial shortening of concrete structures

High density development has been seen as a contribution to sustainable development. However, a number of engineering issues play a crucial role in the sustainable construction of high rise buildings. Non linear deformation of concrete has an adverse impact on high-rise buildings with complex geometries, due to differential axial shortening. These adverse effects are caused by time dependent behaviour resulting in volume change known as ‘shrinkage’, ‘creep’ and ‘elastic’ deformation. These three phenomena govern the behaviour and performance of all concrete elements, during and after construction. Reinforcement content, variable concrete modulus, volume to surface area ratio of the elements, environmental conditions, and construction quality and sequence influence on the performance of concrete elements and differential axial shortening will occur in all structural systems. Its detrimental effects escalate with increasing height and non vertical load paths resulting from geometric complexity. The magnitude of these effects has a significant impact on building envelopes, building services, secondary systems, and lifetime serviceability and performance. Analytical and test procedures available to quantify the magnitude of these effects are limited to a very few parameters and are not adequately rigorous to capture the complexity of true time dependent material response. With this in mind, a research project has been undertaken to develop an accurate numerical procedure to quantify the differential axial shortening of structural elements. The procedure has been successfully applied to quantify the differential axial shortening of a high rise building, and the important capabilities available in the procedure have been discussed. A new practical concept, based on the variation of vibration characteristic of structure during and after construction and used to quantify the axial shortening and assess the performance of structure, is presented.

Bootstrap approaches for estimation and confidence intervals of long term memory processes

In this work, we investigate an alternative bootstrap approach based on a result of Ramsey [F.L. Ramsey, Characterization of the partial autocorrelation function, Ann. Statist. 2 (1974), pp. 1296-1301] and on the Durbin-Levinson algorithm to obtain a surrogate series from linear Gaussian processes with long range dependence. We compare this bootstrap method with other existing procedures in a wide Monte Carlo experiment by estimating, parametrically and semi-parametrically, the memory parameter d. We consider Gaussian and non-Gaussian processes to prove the robustness of the method to deviations from normality. The approach is also useful to estimate confidence intervals for the memory parameter d by improving the coverage level of the interval.

Jack's Bay (the architecturalisation of memory)

Jack's Bay (the architecturalisation of memory) is a key work of the author's exhibition Lightsite, which toured Western Australian galleries from February 2006 to November 2007. It is a five-minute-long exposure photographic image captured inside a purpose-built, room-sized pinhole camera which is demountable and does not have a floor. The work depicts octogenarian Jack Morris, who for forty years held the professional salmon fishing license in the hamlet of Bremer Bay, on the SE coast of Western Australia. The pinhole camera-room is sited within sand dunes new Jack's now demolished beachside camp. Three generations of Jack's descendents stand outside the room - from his daughter to his great grand children. The light from this exterior landscape is 'projected' inside the camera-room and illuminates the interior scene which includes that part of the sand dune upon which the floorless room is erected, along with Jack who is sitting inside. The image evokes the temporality of light. Here, light itself is portrayed as the primary medium through which we both perceive and describe landscape. In this way it is through the agency of light that we construct our connectivity to landscape.

Fusionless scoliosis correction using shape memory alloy staples

Severe spinal deformity in young children is a formidable challenge for optimal treatment. Standard interventions for adolescents, such as spinal deformity correction and fusion, may not be appropriate for young patients with considerable growth remaining. Alternative surgical options that provide deformity correction and protect the growth remaining in the spine are needed to treat this group of patients 1, 2. One such method is the use of shape memory alloy staples. We report our experience to date using video-assisted thoracoscopic insertion of shape memory alloy staples. A retrospective review was conducted of 13 patients with scoliosis, aged 7 to 13 years, who underwent video-assisted thoracoscopic insertion of shape memory staples. In our experience, video-assisted thoracoscopic insertion of shape memory alloy staples is a safe procedure with no complications noted. It is a reliable method of providing curve stability, however the follow up results to date indicate that the effectiveness of the procedure is greater in younger patients.

Fuzzy associative memory for humanoid robot joint control

Traditional approaches to joint control required accurate modelling of the system dynamic of the plant in question. Fuzzy Associative Memory (FAM) control schemes allow adequate control without a model of the system to be controlled. This paper presents a FAM based joint controller implemented on a humanoid robot. An empirically tuned PI velocity control loop is augmented with this feed forward FAM, with considerable reduction in joint position error achieved online and with minimal additional computational overhead.

Low-dimensional hydrogen-bonded structures in the 1:1 and 1:2 proton-transfer compounds of 4,5-dichlorophthalic acid with the aliphatic Lewis bases triethylamine, diethylamine, n-butylamine and piperidine

The structures of proton-transfer compounds of 4,5-dichlorophthalic acid (DCPA) with the aliphatic Lewis bases triethylamine, diethylamine, n-butylamine and piperidine, namely triethylaminium 2-carboxy-4,5-dichlorobenzoate C~6~H~16~N^+^ C~8~H~3~Cl~2~O~4~^-^ (I), diethylaminium 2-carboxy-4,5-dichlorobenzoate C~4~H~12~N^+^ C~8~H~3~Cl~2~O~4~^-^ (II), bis(n-butylaminium) 4,5-dichlorophthalate monohydrate 2(C~4~H~12~N^+^) C~8~H~2~Cl~2~O~4~^2-^ . H~2~O (III) and bis(piperidinium) 4,5-dichlorophthalate monohydrate 2(C~5~H~12~N^+^) C~8~H~2~Cl~2~O~4~^2-^ . H~2~O (IV)have been determined at 200 K. All compounds have hydrogen-bonding associations giving in (I) discrete cation-anion units, linear chains in (II) while (III) and (IV) both have two-dimensional structures. In (I) a discrete cation-anion unit is formed through an asymmetric R2/1(4) N+-H...O,O' hydrogen-bonding association whereas in (II), one-dimensional chains are formed through linear N-H...O associations by both aminium H donors. In compounds (III) and (IV) the primary N-H...O linked cation-anion units are extended into a two-dimensional sheet structure via amide N-H...O(carboxyl) and ...O(carbonyl) interactions. In the 1:1 salts [(I) and (II)], the hydrogen 4,5-dichlorophthalate anions are essentially planar with short intramolecular carboxylic acid O-H...O(carboxyl) hydrogen bonds [O...O, 2.4223(14) and 2.388(2)A respectively]. This work provides a further example of the uncommon zero-dimensional hydrogen-bonded DCPA-Lewis base salt and the one-dimensional chain structure type, while even with the hydrate structures of the 1:2 salts with the primary and secondary amines, the low dimensionality generally associated with 1:1 DCPA salts is also found.

Mediatisation and institutions of public memory : digital storytelling and the apology

Institutions of public memory are increasingly undertaking co-creative media initiatives in which community members create content with the support of institutional expertise and resources. This paper discusses one such initiative: the State Library of Queensland’s ‘Responses to the Apology’, which used a collaborative digital storytelling methodology to co-produce seven short videos capturing individual responses to Prime Minister Kevin Rudd’s 2008 ‘Apology to Australia’s Indigenous Peoples’. In examining this program, we are interested not only in the juxtaposition of ‘ordinary’ responses to an ‘official’ event, but also in how the production and display of these stories might also demonstrate a larger mediatisation of public memory.

Improved correlation-based modal strain energy method for global damage detection of truss bridge structures

The previous investigations have shown that the modal strain energy correlation method, MSEC, could successfully identify the damage of truss bridge structures. However, it has to incorporate the sensitivity matrix to estimate damage and is not reliable in certain damage detection cases. This paper presents an improved MSEC method where the prediction of modal strain energy change vector is differently obtained by running the eigensolutions on-line in optimisation iterations. The particular trail damage treatment group maximising the fitness function close to unity is identified as the detected damage location. This improvement is then compared with the original MSEC method along with other typical correlation-based methods on the finite element model of a simple truss bridge. The contributions to damage detection accuracy of each considered mode is also weighed and discussed. The iterative searching process is operated by using genetic algorithm. The results demonstrate that the improved MSEC method suffices the demand in detecting the damage of truss bridge structures, even when noised measurement is considered.

Damage detection for truss bridge structures using correlation-based structural modal strain energy

This paper presents the feasibility of using structural modal strain energy as a parameter employed in correlation- based damage detection method for truss bridge structures. It is an extension of the damage detection method adopting multiple damage location assurance criterion. In this paper, the sensitivity of modal strain energy to damage obtained from the analytical model is incorporated into the correlation objective function. Firstly, the sensitivity matrix of modal strain energy to damage is conducted offline, and for an arbitrary damage case, the correlation coefficient (objective function) is calculated by multiplying the sensitivity matrix and damage vector. Then, a genetic algorithm is used to iteratively search the damage vector maximising the correlation between the corresponding modal strain energy change (hypothesised) and its counterpart in measurement. The proposed method is simulated and compared with the conventional methods, e.g. frequency-error method, coordinate modal assurance criterion and multiple damage location assurance criterion using mode shapes on a numerical truss bridge structure. The result demonstrates the modal strain energy correlation method is able to yield acceptable damage detection outcomes with less computing efforts, even in a noise contaminated condition.

Design methods of rhombic tensegrity structures

As a special type of novel flexible structures, tensegrity holds promise for many potential applications in such fields as materials science, biomechanics, civil and aerospace engineering. Rhombic systems are an important class of tensegrity structures, in which each bar constitutes the longest diagonal of a rhombus of four strings. In this paper, we address the design methods of rhombic structures based on the idea that many tensegrity structures can be constructed by assembling one-bar elementary cells. By analyzing the properties of rhombic cells, we first develop two novel schemes, namely, direct enumeration scheme and cell-substitution scheme. In addition, a facile and efficient method is presented to integrate several rhombic systems into a larger tensegrity structure. To illustrate the applications of these methods, some novel rhombic tensegrity structures are constructed.

Advanced analysis of steel frame structures comprising non-compact sections

During the past decade, a significant amount of research has been conducted internationally with the aim of developing, implementing, and verifying "advanced analysis" methods suitable for non-linear analysis and design of steel frame structures. Application of these methods permits comprehensive assessment of the actual failure modes and ultimate strengths of structural systems in practical design situations, without resort to simplified elastic methods of analysis and semi-empirical specification equations. Advanced analysis has the potential to extend the creativity of structural engineers and simplify the design process, while ensuring greater economy and more uniform safety with respect to the ultimate limit state. The application of advanced analysis methods has previously been restricted to steel frames comprising only members with compact cross-sections that are not subject to the effects of local buckling. This precluded the use of advanced analysis from the design of steel frames comprising a significant proportion of the most commonly used Australian sections, which are non-compact and subject to the effects of local buckling. This thesis contains a detailed description of research conducted over the past three years in an attempt to extend the scope of advanced analysis by developing methods that include the effects of local buckling in a non-linear analysis formulation, suitable for practical design of steel frames comprising non-compact sections. Two alternative concentrated plasticity formulations are presented in this thesis: the refined plastic hinge method and the pseudo plastic zone method. Both methods implicitly account for the effects of gradual cross-sectional yielding, longitudinal spread of plasticity, initial geometric imperfections, residual stresses, and local buckling. The accuracy and precision of the methods for the analysis of steel frames comprising non-compact sections has been established by comparison with a comprehensive range of analytical benchmark frame solutions. Both the refined plastic hinge and pseudo plastic zone methods are more accurate and precise than the conventional individual member design methods based on elastic analysis and specification equations. For example, the pseudo plastic zone method predicts the ultimate strength of the analytical benchmark frames with an average conservative error of less than one percent, and has an acceptable maximum unconservati_ve error of less than five percent. The pseudo plastic zone model can allow the design capacity to be increased by up to 30 percent for simple frames, mainly due to the consideration of inelastic redistribution. The benefits may be even more significant for complex frames with significant redundancy, which provides greater scope for inelastic redistribution. The analytical benchmark frame solutions were obtained using a distributed plasticity shell finite element model. A detailed description of this model and the results of all the 120 benchmark analyses are provided. The model explicitly accounts for the effects of gradual cross-sectional yielding, longitudinal spread of plasticity, initial geometric imperfections, residual stresses, and local buckling. Its accuracy was verified by comparison with a variety of analytical solutions and the results of three large-scale experimental tests of steel frames comprising non-compact sections. A description of the experimental method and test results is also provided.