Location of hydrogen atoms in hydronium jarosite

Various models for the crystal structure of hydronium jarosite were determined from Rietveld refinements against neutron powder diffraction patterns collected at ambient temperature and also single-crystal X-ray diffraction data. The possibility of a lower symmetry space group for hydronium jarosite that has been suggested by the literature was investigated. It was found the space group is best described as R3¯m, the same for other jarosite minerals. The hydronium oxygen atom was found to occupy the 3¯m site (3a Wyckoff site). Inadequately refined hydronium bond angles and bond distances without the use of restraints are due to thermal motion and disorder of the hydronium hydrogen atoms across numerous orientations. However, the acquired data do not permit a precise determination of these orientations; the main feature up/down disorder of hydronium is clear. Thus, the highest symmetry model with the least disorder necessary to explain all data was chosen: The hydronium hydrogen atoms were modeled to occupy an m (18 h Wyckoff site) with 50 % fractional occupancy, leading to disorder across two orientations. A rigid body description of the hydronium ion rotated by 60° with H–O–H bond angles of 112° and O–H distances of 0.96 Å was optimal. This rigid body refinement suggests that hydrogen bonds between hydronium hydrogen atoms and basal sulfate oxygen atoms are not predominant. Instead, hydrogen bonds are formed between hydronium hydrogen atoms and hydroxyl oxygen atoms. The structure of hydronium alunite is expected to be similar given that alunite supergroup minerals are isostructural.

Structural effects of ammonium and hydronium in jarosite minerals

This thesis resolved the structural ambiguity surrounding ammonium and hydronium ions in the jarosite mineral group. The vibrational spectra of these two minerals were rationalised with their crystal structures for the first time. In doing so, a theory for dealing with orientational disorder in crystals was proposed.

Stepwise refinement of interrupt-driven real-time programs

Embedded real-time programs rely on external interrupts to respond to events in their physical environment in a timely fashion. Formal program verification theories, such as the refinement calculus, are intended for development of sequential, block-structured code and do not allow for asynchronous control constructs such as interrupt service routines. In this article we extend the refinement calculus to support formal development of interrupt-dependent programs. To do this we: use a timed semantics, to support reasoning about the occurrence of interrupts within bounded time intervals; introduce a restricted form of concurrency, to model composition of interrupt service routines with the main program they may preempt; introduce a semantics for shared variables, to model contention for variables accessed by both interrupt service routines and the main program; and use real-time scheduling theory to discharge timing requirements on interruptible program code.

A semi-local method for iterative depth-map refinement

We present an iterative hierarchical algorithm for multi-view stereo. The algorithm attempts to utilise as much contextual information as is available to compute highly accurate and robust depth maps. There are three novel aspects to the approach: 1) firstly we incrementally improve the depth fidelity as the algorithm progresses through the image pyramid; 2) secondly we show how to incorporate visual hull information (when available) to constrain depth searches; and 3) we show how to simultaneously enforce the consistency of the depth-map by continual comparison with neighbouring depth-maps. We show that this approach produces highly accurate depth-maps and, since it is essentially a local method, is both extremely fast and simple to implement.

An examination of the factorial invariance and refinement of the multidimensional school anger inventory for five Pacific Rim countries

The validity of the Multidimensional School Anger Inventory (MSAI) was examined with adolescents from 5 Pacific Rim countries (N ¼ 3,181 adolescents; age, M ¼ 14.8 years; 52% females). Confirmatory factor analyses examined configural invariance for the MSAI’s anger experience, hostility, destructive expression, and anger coping subscales. The model did not converge for Peruvian students. Using the top 4 loaded items for anger experience, hostility, and destructive expression configural invariance and partial metric and scalar invariances were found. Latent means analysis compared mean responses on each subscale to the U.S. sample. Students from other countries showed higher mean responses on the anger experience subscale (ds ¼ .37–.73). Australian (d ¼ .40) and Japanese students (d ¼ .21) had significantly higher mean hostility subscale scores. Australian students had higher mean scores on the destructive expression subscale (d ¼ .30), whereas Japanese students had lower mean scores (d ¼ 2.17). The largest latent mean gender differences (females lower than males) were for destructive expression among Australian (d ¼ 2.67), Guatemalan (d ¼ 2.42), and U.S. (d ¼ 2.66) students. This study supported an abbreviated, 12-item MSAI with partial invariance. Implications for the use of the MSAI in comparative research are discussed.

Selective involvement of TIMP-2 in the second activational cleavage of pro-MMP-2 : refinement of the pro-MMP-2 activation mechanism

A tissue inhibitor of metalloproteinases-2 (TIMP-2)-independent mechanism for generating the first activational cleavage of pro-matrix metalloproteinase-2 (MMP-2) was identified in membrane type-1 MMP (MT1-MMP)-transfected MCF-7 cells and confirmed in TIMP-2-deficient fibroblasts. In contrast, the second MMP-2-activational step was found to be TIMP-2 dependent in both systems. MMP-2 hemopexin C-terminal domain was found to be critical for the first step processing, confirming a need for membrane tethering. We propose that the intermediate species of MMP-2 forms the well-established trimolecular complex (MT1-MMP/TIMP-2/MMP-2) for further TIMP-2-dependent autocatalytic cleavage to the fully active species. This alternate mechanism may supplement the traditional TIMP-2-mediated first step mechanism.

An investigation of goethite-seeded Al(OH)3 precipitation using in situ X-ray diffraction and Rietveld-based quantitative phase analysis

An in situ X-ray diffraction investigation of goethite-seeded Al(OH)3 precipitation from synthetic Bayer liquor at 343 K has been performed. The presence of iron oxides and oxyhydroxides in the Bayer process has implications for alumina reversion, which causes significant process losses through unwanted gibbsite precipitation, and is also relevant for the nucleation and growth of scale on mild steel process equipment. The gibbsite, bayerite and nordstrandite polymorphs of Al(OH)3 precipitated from the liquor; gibbsite appeared to precipitate first, with subsequent formation of bayerite and nordstrandite. A Rietveld-based approach to quantitative phase analysis was implemented for the determination of absolute phase abundances as a function of time, from which kinetic information for the formation of the Al(OH)3 phases was determined.

Model refinement through high-performance computing: an agent-based HIV example

Background Recent advances in Immunology highlighted the importance of local properties on the overall progression of HIV infection. In particular, the gastrointestinal tract is seen as a key area during early infection, and the massive cell depletion associated with it may influence subsequent disease progression. This motivated the development of a large-scale agent-based model. Results Lymph nodes are explicitly implemented, and considerations on parallel computing permit large simulations and the inclusion of local features. The results obtained show that GI tract inclusion in the model leads to an accelerated disease progression, during both the early stages and the long-term evolution, compared to a theoretical, uniform model. Conclusions These results confirm the potential of treatment policies currently under investigation, which focus on this region. They also highlight the potential of this modelling framework, incorporating both agent-based and network-based components, in the context of complex systems where scaling-up alone does not result in models providing additional insights.

The development and refinement of the practice domain framework as a conceptual tool for understanding and guiding social care practice

This study identified the common factors that influence social care practice across disciplines (such as social work and psychology), practice fields, and geographical contexts and further developed the Practice Domain Framework as an empirically-based conceptual framework to assist practitioners in understanding practice complexities. The framework has application in critical reflection, professional supervision, interdisciplinary understanding, teamwork, management, teaching and research. A mixed-methods design was used to identify the components and structure of the refined framework. Eighteen influential factors were identified and organised into eight domains: the Societal, Structural, Organisational, Practice Field, Professional Practice, Accountable Practice, Community of Place, and Personal.