Structure, magnetism and colour in simple bis­(phosphine)nickel(II) dihalide complexes : an experimental and theoretical investigation

The complex [1,2-bis­(di-tert-butyl­phosphan­yl)ethane-[kappa]2P,P']di­iodido­nickel(II), [NiI2(C18H40P2] or (dtbpe-[kappa]2P)NiI2, [dtbpe is 1,2-bis­(di-tert-butyl­phosphan­yl)ethane], is bright blue-green in the solid state and in solution, but, contrary to the structure predicted for a blue or green nickel(II) bis­(phos­phine) complex, it is found to be close to square planar in the solid state. The solution structure is deduced to be similar, because the optical spectra measured in solution and in the solid state contain similar absorptions. In solution at room temperature, no 31P{1H} NMR resonance is observed, but the very small solid-state magnetic moment at temperatures down to 4 K indicates that the weak paramagnetism of this nickel(II) complex can be ascribed to temperature independent paramagnetism, and that the complex has no unpaired electrons. The red [1,2-bis­(di-tert-butyl­phosphan­yl)ethane-[kappa]2P,P']di­chlorido­nickel(II), [NiCl2(C18H40P2] or (dtbpe-[kappa]2P)NiCl2, is very close to square planar and very weakly paramagnetic in the solid state and in solution, while the maroon [1,2-bis­(di-tert-butyl­phosphan­yl)ethane-[kappa]2P,P']di­bromido­nickel(II), [NiBr2(C18H40P2] or (dtbpe-[kappa]2P)NiBr2, is isostructural with the diiodide in the solid state, and displays paramagnetism inter­mediate between that of the dichloride and the diiodide in the solid state and in solution. Density functional calculations demonstrate that distortion from an ideal square plane for these complexes occurs on a flat potential energy surface. The calculations reproduce the observed structures and colours, and explain the trends observed for these and similar complexes. Although theoretical investigation identified magnetic-dipole-allowed excitations that are characteristic for temperature-independent paramagnetism (TIP), theory predicts the mol­ecules to be diamagnetic.

Measuring exposure to solar ultraviolet radiation using a dosimetric technique : understanding participant compliance issues

Personal ultraviolet dosimeters have been used in epidemiological studies to understand the risks and benefits of individuals' exposure to solar ultraviolet radiation (UVR). We investigated the types and determinants of non-compliance associated with a protocol for use of polysulphone UVR dosimeters. In the AusD Study, 1,002 Australian adults (aged 18-75 years) were asked to wear a new dosimeter on their wrist each day for 10 consecutive days to quantify their daily exposure to solar UVR. Of the 10,020 dosimeters distributed, 296 (3%) were not returned or used (Type I non-compliance) and other usage errors were reported for 763 (8%) returned dosimeters (Type II non-compliance). Type I errors were more common in participants with predominantly outdoor occupations. Type II errors were reported more frequently on the first day of measurement; weekend days or rainy days; and among females; younger people; more educated participants or those with outdoor occupations. Half (50%) the participants reported a non-compliance error on at least one day during the 10-day period. However, 92% of participants had at least 7 days of usable data without any apparent non-compliance issues. The factors identified should be considered when designing future UVR dosimetry studies.

The contributions of solar ultraviolet radiation exposure and other determinants to Serum 25-Hydroxyvitamin D concentrations in Australian adults : the AusD study

The Quantitative Assessment of Solar UV [ultraviolet] Exposure for Vitamin D Synthesis in Australian Adults (AusD) Study aimed to better define the relationship between sun exposure and serum 25-hydroxyvitamin D (25(OH)D) concentration. Cross-sectional data were collected between May 2009 and December 2010 from 1,002 participants aged 18-75 years in 4 Australian sites spanning 24° of latitude. Participants completed the following: 1) questionnaires on sun exposure, dietary vitamin D intake, and vitamin D supplementation; 2) 10 days of personal ultraviolet radiation dosimetry; 3) a sun exposure and physical activity diary; and 4) clinical measurements and blood collection for 25(OH)D determination. Our multiple regression model described 40% of the variance in 25(OH)D concentration; modifiable behavioral factors contributed 52% of the explained variance, and environmental and demographic or constitutional variables contributed 38% and 10%, respectively. The amount of skin exposed was the single strongest contributor to the explained variance (27%), followed by location (20%), season (17%), personal ultraviolet radiation exposure (8%), vitamin D supplementation (7%), body mass index (weight (kg)/height (m)2) (4%), and physical activity (4%). Modifiable behavioral factors strongly influence serum 25(OH)D concentrations in Australian adults. In addition, latitude was a strong determinant of the relative contribution of different behavioral factors.

Polymorphisms in inflammation pathway genes and endometrial cancer risk

BACKGROUND Experimental and epidemiologic evidence have suggested that chronic inflammation may play a critical role in endometrial carcinogenesis. METHODS To investigate this hypothesis, a two-stage study was carried out to evaluate single-nucleotide polymorphisms (SNP) in inflammatory pathway genes in association with endometrial cancer risk. In stage I, 64 candidate pathway genes were identified and 4,542 directly genotyped or imputed SNPs were analyzed among 832 endometrial cancer cases and 2,049 controls, using data from the Shanghai Endometrial Cancer Genetics Study. Linkage disequilibrium of stage I SNPs significantly associated with endometrial cancer (P < 0.05) indicated that the majority of associations could be linked to one of 24 distinct loci. One SNP from each of the 24 loci was then selected for follow-up genotyping. Of these, 21 SNPs were successfully designed and genotyped in stage II, which consisted of 10 additional studies including 6,604 endometrial cancer cases and 8,511 controls. RESULTS Five of the 21 SNPs had significant allelic odds ratios (ORs) and 95% confidence intervals (CI) as follows: FABP1, 0.92 (0.85-0.99); CXCL3, 1.16 (1.05-1.29); IL6, 1.08 (1.00-1.17); MSR1, 0.90 (0.82-0.98); and MMP9, 0.91 (0.87-0.97). Two of these polymorphisms were independently significant in the replication sample (rs352038 in CXCL3 and rs3918249 in MMP9). The association for the MMP9 polymorphism remained significant after Bonferroni correction and showed a significant association with endometrial cancer in both Asian- and European-ancestry samples. CONCLUSIONS These findings lend support to the hypothesis that genetic polymorphisms in genes involved in the inflammatory pathway may contribute to genetic susceptibility to endometrial cancer. Impact statement: This study adds to the growing evidence that inflammation plays an important role in endometrial carcinogenesis.

Teaching and assessing ethics and social responsibility in undergraduate science : a position paper

Institutional graduate capabilities and discipline threshold learning outcomes require science students to demonstrate ethical conduct and social responsibility. However, neither the teaching nor the assessment of these concepts is straightforward. Australian chemistry academics participated in a workshop in 2013 to discuss and develop teaching and assessment in these areas and this paper reports on the outcomes of that workshop. Controversial issues discussed included: How broad is the mandate of the teacher, how should the boundaries between personal values and ethics be drawn, and how can ethics be assessed without moral judgement? In this position paper, I argue for a deep engagement with ethics and social justice, achieved through case studies and assessed against criteria that require discussion and debate. Strategies to effectively assess science students’ understanding of ethics and social responsibility are detailed.

An intervention to discourage Australian mothers from unnecessarily exposing their babies to the sun for therapeutic reasons

Parents play a key role in children’s sun-protective behaviour, with good sun-protective habits established early tending to be sustained. We designed a maternity hospital-based educational intervention to reduce myths that could result in mothers intentionally sunning their babies. Interviews were conducted with two cross-sections of healthy post-partum inpatients in the maternity ward of a large regional public hospital. The first group (n¼106) was recruited before the commencement of educational in-services for maternity nursing staff; the second group (n¼203) was interviewed after the last staff in-service session. More pre-intervention than post-intervention women reported they would expose their baby to sunlight to: treat suspected jaundice (28.8% vs. 13.3%; p<0.001) or help their baby’s skin adapt to sunlight (10.5% vs. 2.5%; p¼0.003). Fewer post-intervention women indicated they would sun themselves to treat breastfeeding-associated sore/cracked nipples (7.6% vs. 2%; p¼0.026). This educational intervention should be used to educate parents, health professionals and students

Responsible reconstruction : The architect's role

This paper investigates the role of the architect in post-disaster reconstruction and questions their ability to facilitate per- manent building solutions. There is an ever-increasing population of refugees and internally displaced persons due to disasters and conflicts who have a basic need for shelter. To date, housing solutions for such people has tended to focus on short-term, temporary shelter solutions that have been largely unsuccessful. This increasing demand for shelter has led to an emerging group of architects skilled in post-disaster reconstruction. These architects acknowledge that shelter is critical to survival, but believe architects should focus on rebuilding in a manner that is quick, durable but permanent. They believe that an architect skilled in post-disaster reconstruction can produce solutions that meet the requirement of the emergency phase, through to semi-permanent and even permanent homes, without wasting time and money on interim shelters. Case Study Research was used to examine and evaluate the assistance provided by Emergency Architects Australia (EAA) to the Kei Gold community in the Solomon Islands after the 2007 earthquake and tsunami. The results indicate that an architect’s response to a disaster must go beyond providing temporary shelter; they must create permanent building solutions that respond to the site and the culture while servicing the needs of the communi- ty. The vernacular reconstruction methods implemented by EAA in Kei Gold Village have been successful in develop- ing permanent housing solutions. Further research and development is required to gain a broader understanding of the role of the architect in disasters of varying scales and typologies.

Deriving a preference-based utility measure for cancer patients from the European Organisation for the Research and Treatment of Cancer's Quality of Life Questionnaire C30 : a confirmatory versus exploratory approach

Background Multi attribute utility instruments (MAUIs) are preference-based measures that comprise a health state classification system (HSCS) and a scoring algorithm that assigns a utility value to each health state in the HSCS. When developing a MAUI from a health-related quality of life (HRQOL) questionnaire, first a HSCS must be derived. This typically involves selecting a subset of domains and items because HRQOL questionnaires typically have too many items to be amendable to the valuation task required to develop the scoring algorithm for a MAUI. Currently, exploratory factor analysis (EFA) followed by Rasch analysis is recommended for deriving a MAUI from a HRQOL measure. Aim To determine whether confirmatory factor analysis (CFA) is more appropriate and efficient than EFA to derive a HSCS from the European Organisation for the Research and Treatment of Cancer’s core HRQOL questionnaire, Quality of Life Questionnaire (QLQ-C30), given its well-established domain structure. Methods QLQ-C30 (Version 3) data were collected from 356 patients receiving palliative radiotherapy for recurrent/metastatic cancer (various primary sites). The dimensional structure of the QLQ-C30 was tested with EFA and CFA, the latter informed by the established QLQ-C30 structure and views of both patients and clinicians on which are the most relevant items. Dimensions determined by EFA or CFA were then subjected to Rasch analysis. Results CFA results generally supported the proposed QLQ-C30 structure (comparative fit index =0.99, Tucker–Lewis index =0.99, root mean square error of approximation =0.04). EFA revealed fewer factors and some items cross-loaded on multiple factors. Further assessment of dimensionality with Rasch analysis allowed better alignment of the EFA dimensions with those detected by CFA. Conclusion CFA was more appropriate and efficient than EFA in producing clinically interpretable results for the HSCS for a proposed new cancer-specific MAUI. Our findings suggest that CFA should be recommended generally when deriving a preference-based measure from a HRQOL measure that has an established domain structure.

Influences of molecular structure on co-crystallization of polypyridyl metal complexes.

Heteroleptic complexes of the type \[RuL2L′](PF6)2 (L, L′ = combinations of 1,10-phenanthroline (phen) and 2,2′-bipyridine (bipy)) were found to cocrystallize with \[Ni(phen)3](PF6)2 to produce cocrystals of \[Ni(phen)3]x\[RuL2L′]1–x(PF6)2. In this report we show that the ability of the complexes to cocrystallize is influenced by the number of common ligands between complexes in solution. Supramolecular selection is a phenomenon caused by molecular recognition through which cocrystals can grow from the same solution but contain different ratios of the molecular components. It was found that systems where L = phen displayed less supramolecular selection than systems where L = bipy. With increasing supramolecular selection, the composition of cocrystals was found to vary significantly from the initial relative concentration in the cocrystallizing solution, and therefore it was increasingly difficult to control the final composition of the resultant cocrystals. Consequently, modulation of concentration-dependent properties such as phase was also found to be less predictable with increasing supramolecular selection. Notwithstanding the complication afforded by the presence of supramolecular selection, our results reaffirm the robustness of the \[M(phen)3](PF6)2 structure because it was maintained even when ca. 90% of the complexes in the cocrystals were \[Ru(phen)(bipy)2](PF6)2, which in its pure form is not isomorphous with \[M(phen)3](PF6)2. Experiments between complexes without common ligands, i.e., \[Ru(bipy)3](PF6)2 cocrystallized with \[Ni(phen)3](PF6)2, were found to approach the limit to which molecular recognition processes can be confused into cocrystallizing different molecules to form single cocrystals. For these systems the result was the formation of block-shaped crystals skewered by a needle-shaped crystals.

Exploring internal communication's impact on psychological contract currencies

Internal communication is a central process by which employees exchange information, build relationships and share organisational values. Fundamental to this process is the psychological contract. However, there is limited understanding of how internal communication influences psychological contract. The study contributes to theory by demonstrating that the dimensions of internal communication independently influence internal stakeholders' psychological contract beliefs. For managers, the findings can be used as a framework to improve internal communication processes and strategies.

Life cycle energy analysis of eight residential houses in Brisbane, Australia

Life cycle energy analysis (LCEA) of eight residential buildings in and around Brisbane, Queensland, Australia, is undertaken in this study. Energy used in all three phases of construction, operation and demolition are considered. It is found that the main contribution to the operational energy in residential buildings is from use of general appliance. The choice of building materials is shown to have significant effects on the embodied energy for the production, construction, maintenance and demolition phases. From this study, it is shown that the embodied energy may vary from 10% to 30%, while the operational energy may vary from 65% to 90%. The demolition energy generally accounts for less than 4% of life cycle energy.

Reproductive interference between honey bee species in artificial sympatry

Reproductive isolation between closely related species is often incomplete. The Western honey bee, Apis mellifera, and the Eastern hive bee, A. cerana have been allopatric for millions of years, but are nonetheless similar in morphology and behaviour. During the last century the two species were brought into contact anthropogenically, providing potential opportunities for interspecific matings. Hybrids between A. mellifera and A. cerana are inviable, so natural interspecific matings are of concern because they may reduce the viability of A. cerana and A. mellifera populations – two of the world's most important pollinators. We examined the mating behaviour of A. mellifera and A. cerana queens and drones from Caoba Basin, China and Cairns, Australia. Drone mating flight times overlap in both areas. Analysis of the spermathecal contents of queens with species-specific genetic markers indicated that in Caoba Basin, 14% of A. mellifera queens mated with at least one A. cerana male, but we detected no A. cerana queens that had mated with A. mellifera males. Similarly, in Cairns, no A. cerana queens carried A. mellifera sperm, but one third of A. mellifera queens had mated with at least one A. cerana male. No hybrid embryos were detected in eggs laid by interspecifically-mated A. mellifera queens in either location. However A. mellifera queens artificially inseminated with A. cerana sperm produced inviable hybrid eggs, or unfertilised drones. This suggests that reproductive interference will impact the viability of honey bee populations wherever A. cerana and A. mellifera are in contact. This article is protected by copyright. All rights reserved.

Variações sobre liberdade: estudo do conceito de liberdade no pensamento metafísico de Descartes

O objetivo desta dissertação é examinar alguns aspectos da doutrina da liberdade humana no pensamento metafísico de Descartes. Através do exame do conceito cartesiano da liberdade humana nas Meditações, nos Princípios e na correspondência com Mesland, pretende-se averiguar se Descartes modifica esse conceito ao longo de sua obra e, por conseguinte, se é possível ou não aceitar a tese da evolução deste conceito. A abordagem de tal questão leva em conta, além da análise dos textos de Descartes, as interpretações mais representativas sobre o assunto.