meso-Porphyrinylphosphine Oxides: Mono- and Bidentate Ligands for Supramolecular Chemistry and the Crystal Structures of Monomeric [10,20-Diphenylporphyrinatonickel(II)-5,15-diyl]-bis-[P(O)Ph2] and Polymeric Self-Coordinated ([10,20-Diphenylporphyrinatozinc(II)-5,15-diyl]-bis-[P(O)Ph2])

A series of porphyrins substituted in one or two meso-positions by diphenylphosphine oxide groups has been prepared by the palladium catalysed reaction of diphenylphosphine or its oxide with the corresponding bromoporphyrins. Compounds {MDPP-[P(O)Ph2]n} (M = H2, Ni, Zn; H2DPP = 5,15-diphenylporphyrin; n = 1, 2) were isolated in yields of 60-95%. The reaction is believed to proceed via the conventional oxidative addition, phosphination and reductive elimination steps, as the stoichiometric reaction of η1-palladio(II) porphyrin [PdBr(H2DPP)(dppe)] (H2DPP = 5,15-diphenylporphyrin; dppe = 1,2-bis(diphenylphosphino)ethane) with diphenylphosphine oxide also results in the desired mono-porphyrinylphosphine oxide [H2DPP-P(O)Ph2]. Attempts to isolate the tertiary phosphines failed due to their extreme air-sensitivity. Variable temperature 1H NMR studies of [H2DPP-P(O)Ph2] revealed an intrinsic lack of symmetry, while fluorescence spectroscopy showed that the phosphine oxide group does not behave as a "heavy atom" quencher. The electron withdrawing effect of the phosphine oxide group was confirmed by voltammetry. The ligands were characterised by multinuclear NMR and UV-visible spectroscopy as well as mass spectrometry. Single crystal X-ray crystallography showed that the bis(phosphine oxide) nickel(II) complex {[NiDPP-[P(O)Ph2]2} is monomeric in the solid state, with a ruffled porphyrin core and the two P=O fragments on the same side of the average plane of the molecule. On the other hand, the corresponding zinc(II) complex formed infinite chains through coordination of one Ph2PO substituent to the neighbouring zinc porphyrin through an almost linear P=O---Zn unit, leaving the other Ph2PO group facing into a parallel channel filled with disordered water molecules. These new phosphine oxides are attractive ligands for supramolecular porphyrin chemistry.

Role demands and work-family balance experience in Malaysia : the different moderating effects of collectivism and gender role identity among diverse ethnic groups

The purpose of this thesis is to examine the influence of ethnic cultural values on the relationship of role demands and the work-family balance (WFB) experience. Past studies have found that the demands from work and family roles have a different impact on the work-family experience in people of different ethnicity. Researchers attribute these results to the cultural differences across the groups. However, there has been no empirical support for these assumptions because most past studies did not explicitly measure the cultural dimension in their design. Therefore, although studies have found ethnic differences in work-family experience, as cultural variables were not measured, it cannot be determined whether these differences were due to the differing ethnic groups’ cultural styles. The present thesis is set up to address this limitation in the literature, employing the Malay and Chinese ethnic groups in Malaysia as the study samples. The investigation consisted of pilot interviews and two survey studies. The interviews were carried out to establish the perception of WFB by target participants of a non-western nation. The first survey served to identify whether the Malay and Chinese ethnic groups residing under the same economic and social systems vary in their perceptions of work and family roles. The second survey tests the research model empirically, that is, whether cultural values moderate the relationship between role demands and WFB and if these moderation effects vary across ethnic groups. From the interviews, the results indicated that work-family experience is not a universal experience, but is partly culture-specific. Specifically, in the case of Malaysia, WFB is very much observed from the role obligation perspective. In particular, balance is perceived when work duties and household affairs are both adequately fulfilled. On the other hand, the conceptualisation of WFB in terms of role satisfaction and role interference also emerged in the interviews, suggesting the universality of these constructs across cultures. The findings from Survey One indicated that participants of different ethnicities in this study do not differ greatly in their perceptions regarding their participation in work and family roles. Generally, these participants revealed the less traditional attitudes towards women’s participation in work and family roles. However, variations were observed between the two groups in terms of reasons for working, spouses’ preferences towards their employment, and the extent to which their work role is perceived to impede their normative role performance in the household. Despite these differences, the Malay and Chinese ethnic groups showed more similarities than differences in their perceptions of work and family. The findings from Survey Two, which tested the research model, produced mixed results. On the whole, the results showed that the cultural dimensions examined in this study (i.e. collectivism, work identity and family identity) did influence the relationship between role demands and WFB experience, thus providing empirical evidence for the assumption in the literature that the relationship between role demand and work-family experience is moderated by cultural values. Most importantly, support was found for the proposition that these moderation effects vary between the Malay and Chinese ethnic groups. Moreover, this study also found evidence that Malays and Chinese differ significantly on collectivism and work identity cultural dimensions where Malays are found to be more collectivist than the Chinese, while work identity is stronger in the Chinese than in the Malays. There is no difference in the levels of family identity between the two groups. Of all the three moderators, work identity was deemed the most important because many of the supported hypotheses pertained to the work identity moderating effects. In contrast, family identity does not seem to have much moderating influence on role demand-WFB relationships, while the results for the collectivism moderator are mixed. As such, although not conclusive, it can be deduced that variations in the effects of role demand on work-family experience across ethnicity are a result of the groups’ cultural differences, thereby supporting the assumption in the literature.

Working in online groups-the challenges of virtually integrated learning environments

Universities continue to struggle with the need to combine the pedagogical benefits of collaborative learning with large scale, interactive and technologically sophisticated learning and teaching arrproaches and support systems. This challenge requires imaginative approaches if the outcome is not to the 'worst of both worlds' that results in confusion and disillusionism amongst students. This paper presents three case studies that use online technologies to provide collaborative teaching solutions arguably much superior to that possible without an online intervention.

A Raman spectroscopic study of the different vanadate-groups in solid-state compounds, model case : mineral phases vésigniéite, BaCu3(VO4)2(OH)2, and volborthite, Cu3V2O7(OH)2•2H2O

Raman spectroscopy has been used to study vanadates in the solid state. The molecular structure of the vanadate minerals vésigniéite [BaCu3(VO4)2(OH)2] and volborthite [Cu3V2O7(OH)2·2H2O] have been studied by Raman spectroscopy and infrared spectroscopy. The spectra are related to the structure of the two minerals. The Raman spectrum of vésigniéite is characterized by two intense bands at 821 and 856 cm−1 assigned to ν1 (VO4)3− symmetric stretching modes. A series of infrared bands at 755, 787 and 899 cm−1 are assigned to the ν3 (VO4)3− antisymmetric stretching vibrational mode. Raman bands at 307 and 332 cm−1 and at 466 and 511 cm−1 are assigned to the ν2 and ν4 (VO4)3− bending modes. The Raman spectrum of volborthite is characterized by the strong band at 888 cm−1, assigned to the ν1 (VO3) symmetric stretching vibrations. Raman bands at 858 and 749 cm−1 are assigned to the ν3 (VO3) antisymmetric stretching vibrations; those at 814 cm−1 to the ν3 (VOV) antisymmetric vibrations; that at 508 cm−1 to the ν1 (VOV) symmetric stretching vibration and those at 442 and 476 cm−1 and 347 and 308 cm−1 to the ν4 (VO3) and ν2 (VO3) bending vibrations, respectively. The spectra of vésigniéite and volborthite are similar, especially in the region of skeletal vibrations, even though their crystal structures differ.

Community protest groups' perceptions of environmental risks using social contagion theory

Local communities are vulnerable to the potential environmental risks associated with construction activity. Currently, little is understood about how perceptions of environmental risks are shaped and spread within a community. A better understanding of this process can help bridge the gap between developers and communities and bring about more sustainable development practices. This paper reports a research methodology which uses social contagion theory to investigate this process. The research adopts a single case study approach of a highly controversial housing project in the greater Sydney metropolitan area. The case study is particularly significant as it investigates an extensive and on-going community-based protest campaign (dating back almost 20 years) that has generated the longest standing 24 hour community picket in the New South Wales.

Vulnerable road user groups : a review of younger drivers, motorcyclists and older drivers

Scientific efforts to understand and reduce the occurrence of road crashes continue to expand, particularly in the areas of vulnerable road user groups. Three groups that are receiving increasing attention within the literature are younger drivers, motorcyclists and older drivers. These three groups are at an elevated risk of being in a crash or seriously injured, and research continues to focus on the origins of this risk as well as the development of appropriate countermeasures to improve driving outcomes for these cohorts. However, it currently remains unclear what factors produce the largest contribution to crash risk or what countermeasures are likely to produce the greatest long term positive effects on road safety. This paper reviews research that has focused on the personal and environmental factors that increase crash risk for these groups as well as considers direction for future research in the respective areas. A major theme to emerge from this review is that while there is a plethora of individual and situational factors that influence the likelihood of crashes, these factors often combine in an additive manner to exacerbate the risk of both injury and fatality. Additionally, there are a number of risk factors that are pertinent for all three road user groups, particularly age and the level of driving experience. As a result, targeted interventions that address these factors are likely to maximise the flow-on benefits to a wider range of road users. Finally, there is a need for further research that aims to bridge the research-to-practice gap, in order to develop appropriate pathways to ensure that evidenced-based research is directly transferred to effective policies that improve safety outcomes.

Food modelling systems to assess menus in well population groups : not all black and white

Food modelling systems such as the Core Foods and the Australian Guide to Healthy Eating are frequently used as nutritional assessment tools for menus in ‘well’ groups (such as boarding schools, prisons and mental health facilities), with the draft Foundation and Total Diets (FATD) the latest revision. The aim of this paper is to apply the FATD to an assessment of food provision in a long stay, ‘well’, group setting to determine its usefulness as a tool. A detailed menu review was conducted in a 1000 bed male prison, including verification of all recipes. Full diet histories were collected on 106 prisoners which included foods consumed from the menu and self funded snacks. Both the menu and diet histories were analysed according to core foods, with recipes used to assist in quantification of mixed dishes. Comparison was made of average core foods with Foundation Diet recommendations (FDR) for males. Results showed that the standard menu provided sufficient quantity for 8 of 13 FDRs, however was low in nuts, legumes, refined cereals and marginally low in fruits and orange vegetables. The average prisoner diet achieved 9 of 13 FDRs, notably with margarines and oils less than half and legumes one seventh of recommended. Overall, although the menu and prisoner diets could easily be assessed using the FDRs, it was not consistent with recommendations. In long stay settings other Nutrient Reference Values not modelled in the FATDS need consideration, in particular, Suggested Dietary Targets and professional judgement is required in interpretation.

Tracheobronchial and alveolar dose of submicrometer particles for different population age groups in Italy

Exposure to ultrafine particles (diameter less than 100 nm) is an important topic in epidemiological and toxicological studies. This study used the average particle number size distribution data obtained from our measurement survey in major micro-environments, together with the people activity pattern data obtained from the Italian Human Activity Pattern Survey to estimate the tracheobronchial and alveolar dose of submicrometer particles for different population age groups in Italy. We developed a numerical methodology based on Monte Carlo method, in order to estimate the best combination from a probabilistic point of view. More than 106 different cases were analyzed according to a purpose built sub-routine and our results showed that the daily alveolar particle number and surface area deposited for all of the age groups considered was equal to 1.5 x 1011 particles and 2.5 x 1015 m2, respectively, varying slightly for males and females living in Northern or Southern Italy. In terms of tracheobronchial deposition, the corresponding values for daily particle number and surface area for all age groups was equal to 6.5 x 1010 particles and 9.9 x 1014 m2, respectively. Overall, the highest contributions were found to come from indoor cooking (female), working time (male) and transportation (i.e. traffic derived particles) (children).

Cultural impact on e-service use in Saudi Arabia : results from focus groups

This paper reports the results of focus groups obtained as part of a full study that uses a mixed method approach to answer the following question: what are the cultural values that impact on e-service use in Saudi Arabia? In order to answer this question we reviewed culture theories, dimensions, and models that have been identified in the literature. Four focus groups interviewing experts and general users (customers) of online services in Saudi Arabia have been completed aiming at the end to identify the uncovered elements of Saudi culture in the literature, which hopefully will result in developing a framework of cultural values that affect e-service use in Saudi context. This paper will firstly, introduce the importance of culture and define the aspects of Saudi culture. It will then describe the method used, and finally discussing the findings of the focus groups. Findings revealed four factors that have not been covered in the literature and need to be investigated namely: nepotism, the lack of human interaction, services oriented culture, and the career path.