67 resultados para Íon európio(III)
em Queensland University of Technology - ePrints Archive
Resumo:
In 2012, Professor Ian Fletcher (United Kingdom) and Professor Bob Wessels (The Netherlands) presented a Report to the American Law Institute and the International Insolvency Institute entitled Transnational Insolvency: Global Principles for Cooperation in International Insolvency Cases (“Global Principles”). This followed their appointment as Joint Reporters to investigate whether the essential provisions of the American Law Institute Principles of Cooperation among the North American Free Trade Agreement Countries with their annexed Guidelines Applicable to Court-to-Court Communication in Cross-border Cases may, with certain necessary modifications, be acceptable for use by jurisdictions across the world. This article comments on the Global Principles from the perspective of a jurisdiction which has adopted the UNCITRAL Model Law on Cross-border Insolvency (“Model Law”). In 2008, Australia enacted a standalone statute, the Cross-border Insolvency Act 2008 (Cth) to which is annexed the Model Law. In that process, it made minimal changes to the Model Law text. Against the background of the 2008 Act, related procedural laws as well as Australia’s general insolvency statutes and recent cross-border insolvency jurisprudence, this article comments on the potential relevance of the Transnational Insolvency Report as a point of reference for Australian courts and insolvency administrators when addressing international insolvency cases. By comparing the Global Principles with the Model Law as closely adopted in Australia, this analysis is a resource for other Model Law jurisdictions when considering the potential relevance of the Global Principles for their own international insolvency practice.
Resumo:
The electrochemical characteristics of a series of heteroleptic tris(phthalocyaninato) complexes with identical rare earths or mixed rare earths (Pc)M(OOPc)M(OOPc) [M = Eu...Lu, Y; H2Pc = unsubstituted phthalocyanine, H2(OOPc) = 3,4,12,13,21,22,30,31-octakis(octyloxy)phthalocyanine] and (Pc)Eu(OOPc)Er(OOPc) have been recorded and studied comparatively by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in CH2Cl2 containing 0.1 M tetrabutylammonium perchlorate (TBAP). Up to five quasi-reversible one-electron oxidations and four one-electron reductions have been revealed. The half-wave potentials of the first, second and fifth oxidations depend on the size of the metal center, but the fifth changes in the opposite direction to that of the first two. Moreover, the difference in redox potentials of the first oxidation and first reduction for (Pc)M(OOPc)M(OOPc), 0.85−0.98 V, also decreases linearly along with decreasing rare earth ion radius, clearly showing the rare earth ion size effect and indicating enhanced π−π interactions in the triple-deckers connected by smaller lanthanides. This order follows the red-shift seen in the lowest energy band of triple-decker compounds. The electronic differences between the lanthanides and yttrium are more apparent for triple-decker sandwich complexes than for the analogous double-deckers. By comparing triple-decker, double-decker and mononuclear [ZnII] complexes containing the OOPc ligand, the HOMO−LUMO gap has been shown to contract approximately linearly with the number of stacked phthalocyanine ligands.
Resumo:
The electrochemistry of homoleptic substituted phthalocyaninato rare earth double-decker complexes M(TBPc)2 and M(OOPc)2 [M = Y, La...Lu except Pm; H2TBPc = 3(4),12(13),21(22),30(31)-tetra-tert-butylphthalocyanine, H2OOPc = 3,4,12,13,21,22,30,31-octakis(octyloxy)phthalocyanine] has been comparatively studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in CH2Cl2 containing 0.1 M tetra-n-butylammonium perchlorate (TBAP). Two quasi-reversible one-electron oxidations and three or four quasi-reversible one-electron reductions have been revealed for these neutral double-deckers of two series of substituted complexes, respectively. For comparison, unsubstituted bis(phthalocyaninato) rare earth analogues M(Pc)2 (M = Y, La...Lu except Pm; H2Pc = phthalocyanine) have also been electrochemically investigated. Two quasi-reversible one-electron oxidations and up to five quasi-reversible one-electron reductions have been revealed for these neutral double-decker compounds. The three bis(phthalocyaninato)cerium compounds display one cerium-centered redox wave between the first ligand-based oxidation and reduction. The half-wave potentials of the first and second oxidations and first reduction for double-deckers of the tervalent rare earths depend on the size of the metal center. The difference between the redox potentials of the second and third reductions for MIII(Pc)2, which represents the potential difference between the first oxidation and first reduction of [MIII(Pc)2]−, lies in the range 1.08−1.37 V and also gradually diminishes along with the lanthanide contraction, indicating enhanced π−π interactions in the double-deckers connected by the smaller, lanthanides. This corresponds well with the red-shift of the lowest energy band observed in the electronic absorption spectra of reduced double-decker [MIII(Pc′)2]− (Pc′ = Pc, TBPc, OOPc).
Resumo:
We report a theoretical study of the multiple oxidation states (1+, 0, 1−, and 2−) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3‘,5‘-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the “fully delocalized” or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.
Resumo:
This study contributes to the growth of design knowledge in China, where vehicle design for the local, older user is in its initial developmental stages. Therefore, this research has explored the travel needs of older Chinese vehicle users in order to assist designers to better understand users’ current and future needs. A triangulation method consisting of interviews, logbook and co-discovery was used to collect multiple forms of data and so explore the research question. Grounded theory has been employed to analyze the research data. This study found that users’ needs are reflected through various ‘meanings’ that they attach to vehicles – meanings that give a tangible expression to their experiences. This study identified six older-user need categories: (i) safety, (ii) utility, (iii) comfort, (iv) identity, (v) emotion and (vi) spirituality. The interrelationships among these six categories are seen as an interactive structure, rather than as a linear or hierarchical arrangement. Chinese cultural values, which are generated from particular local context and users’ social practice, will play a dynamic role in linking and shaping the travel needs of older vehicle users in the future. Moreover, this study structures the older-user needs model into three levels of meaning, to give guidance to vehicle design direction: (i) the practical meaning level, (ii) the social meaning level and (ii) the cultural meaning level. This study suggests that a more comprehensive explanation exists if designers can identify the vehicle’s meaning and property associated with the fulfilled older users’ needs. However, these needs will vary, and must be related to particular technological, social, and cultural contexts. The significance of this study lies in its contributions to the body of knowledge in three areas: research methodology, theory and design. These theoretical contributions provide a series of methodological tools, models and approaches from a vehicle design perspective. These include a conditional/consequential matrix, a travel needs identification model, an older users’ travel-related needs framework, a user information structure model, and an Older-User-Need-Based vehicle design approach. These models suggest a basic framework for the new design process which might assist in the design of new vehicles to fulfil the needs of future, aging Chinese generations. The models have the potential to be transferred to other design domains and different cultural contexts.
Resumo:
Objective: To examine the reliability of work-related activity coding for injury-related hospitalisations in Australia. Method: A random sample of 4373 injury-related hospital separations from 1 July 2002 to 30 June 2004 were obtained from a stratified random sample of 50 hospitals across 4 states in Australia. From this sample, cases were identified as work-related if they contained an ICD-10-AM work-related activity code (U73) allocated by either: (i) the original coder; (ii) an independent auditor, blinded to the original code; or (iii) a research assistant, blinded to both the original and auditor codes, who reviewed narrative text extracted from the medical record. The concordance of activity coding and number of cases identified as work-related using each method were compared. Results: Of the 4373 cases sampled, 318 cases were identified as being work-related using any of the three methods for identification. The original coder identified 217 and the auditor identified 266 work-related cases (68.2% and 83.6% of the total cases identified, respectively). Around 10% of cases were only identified through the text description review. The original coder and auditor agreed on the assignment of work-relatedness for 68.9% of cases. Conclusions and Implications: The current best estimates of the frequency of hospital admissions for occupational injury underestimate the burden by around 32%. This is a substantial underestimate that has major implications for public policy, and highlights the need for further work on improving the quality and completeness of routine, administrative data sources for a more complete identification of work-related injuries.
Resumo:
Child abuse and neglect is a significant health and social problem with serious consequences for children, families and communities. This chapter provides students, early childhood teachers, and administrators with an evidence base for understanding their role in relation to child abuse and neglect. The chapter draws from international and interdisciplinary research to address four key areas of responsibility: i) recognising signs of child abuse and neglect; ii) reporting child abuse and neglect; iii) supporting children in the classroom; and iv) teaching children to protect themselves (Watts, 1997).
Resumo:
Purpose: In the present work we consider our (in progress) spectroscopy study of zinc and iron phosphates under the influence external high pressure to determine zinc ion change coordination from tetrahedral to octahedral (or hexahedral) structure.----- Design/methodology/approach: The standard equipment is the optical high pressure cell with diamond (DAC). The DAC is assembled and then vibrational or electronic spectra are collected by mounting the cell in an infrared, Raman, EXAFS or UV-visible spectrometer.----- Findings: Mechanism by which zinc and iron methaphosphate material is transformed to glassy meta-phosphate is enhancing mechanical properties of tribofilm. The two decades of intensive study demonstrates that Zn (II) and Fe (III) ions participate to cross-link network under friction, hardening the phosphate.----- Research limitations/implications: Transition metal atoms with d orbital have flexible coordination numbers, for example zinc acts as a cross-linking agent increasing hardness, by changing coordination from tetrahedral to octahedral. Perhaps the external pressure effect on the [Zn–(O-P-)4 ] complex causes a transformation to an [Zn –(O-P-)6] grouping.----- Originality/value: This paper analyses high-pressure spectroscopy which has been applied for the investigation of 3D transition metal ions in solids. When studying pressure effects on coordination compounds structure, we can expect changes in ground electronic state (spin-crossovers), electronic spectra due to structural distortions (piezochromism), and changes in the ligand field causing shifts in the electronic transitions.
Resumo:
EPR study of both blue and green sapphire samples confirms the presence of Cr(III) in four different octahedral sites. The g (1.98) value is the same but D values differ for the two the samples. The EPR spectra suggest that the blue sapphire contains more chromium than the green sapphire. No Fe(III) impurity was noted in the EPR spectrum.
Resumo:
This study compared two popular measures of cognitive ability for preschool children. The Wechsler Preschool and Primary Scale of Intelligence – Third Edition (WPPSI-III) and the Stanford-Binet Intelligence Scale – Fifth Edition (SB5) were administered in a counterbalanced order to 36 typically developing 4-year-old children. There were significant correlations among all WPPSI-III and SB5 composite scores but a small number of children had notable differences between their scores on the two measures. Children tended to prefer the SB5 over the WPPSI-III. Implications for practitioners who assess preschool-aged children are discussed.
Resumo:
The automatic extraction of road features from remote sensed images has been a topic of great interest within the photogrammetric and remote sensing communities for over 3 decades. Although various techniques have been reported in the literature, it is still challenging to efficiently extract the road details with the increasing of image resolution as well as the requirement for accurate and up-to-date road data. In this paper, we will focus on the automatic detection of road lane markings, which are crucial for many applications, including lane level navigation and lane departure warning. The approach consists of four steps: i) data preprocessing, ii) image segmentation and road surface detection, iii) road lane marking extraction based on the generated road surface, and iv) testing and system evaluation. The proposed approach utilized the unsupervised ISODATA image segmentation algorithm, which segments the image into vegetation regions, and road surface based only on the Cb component of YCbCr color space. A shadow detection method based on YCbCr color space is also employed to detect and recover the shadows from the road surface casted by the vehicles and trees. Finally, the lane marking features are detected from the road surface using the histogram clustering. The experiments of applying the proposed method to the aerial imagery dataset of Gympie, Queensland demonstrate the efficiency of the approach.
Resumo:
Road features extraction from remote sensed imagery has been a long-term topic of great interest within the photogrammetry and remote sensing communities for over three decades. The majority of the early work only focused on linear feature detection approaches, with restrictive assumption on image resolution and road appearance. The widely available of high resolution digital aerial images makes it possible to extract sub-road features, e.g. road pavement markings. In this paper, we will focus on the automatic extraction of road lane markings, which are required by various lane-based vehicle applications, such as, autonomous vehicle navigation, and lane departure warning. The proposed approach consists of three phases: i) road centerline extraction from low resolution image, ii) road surface detection in the original image, and iii) pavement marking extraction on the generated road surface. The proposed method was tested on the aerial imagery dataset of the Bruce Highway, Queensland, and the results demonstrate the efficiency of our approach.
Resumo:
Natural iowaite, magnesium–ferric oxychloride mineral having light green color originating from Australia has been characterized by EPR, optical, IR, and Raman spectroscopy. The optical spectrum exhibits a number of electronic bands due to both Fe(III) and Mn(II) ions in iowaite. From EPR studies, the g values are calculated for Fe(III) and g and A values for Mn(II). EPR and optical absorption studies confirm that Fe(III) and Mn(II) are in distorted octahedral geometry. The bands that appear both in NIR and Raman spectra are due to the overtones and combinations of water and carbonate molecules. Thus EPR, optical, and Raman spectroscopy have proven most useful for the study of the chemistry of natural iowaite and chemical changes in the mineral.