Supramolecular selection in molecular alloys

Complexes of the type \[M(phen)3](PF6)2 (M = Ni(II), Fe(II), Ru(II) and phen = 1,10-phenanthroline) were found to co-crystallize to form molecular alloys (solid solutions of molecules) with general formula \[MAxMB1–x(phen)3](PF6)2·0.5H2O in which the relative concentrations of the metal complexes in the crystals closely match those in the crystallizing solution. Consequently, the composition of the co-crystals can be accurately predicted and controlled by modulating the relative concentrations of the metal complexes in the crystallizing solution. Although they are chemically and structurally similar, complexes of the type \[M(bipy)3](PF6)2 (M = Ni(II), Fe(II), Ru(II) and bipy = 2,2′-bipyridine) display markedly different behavior upon co-crystallization. In this case, the resulting co-crystals of general formula \[MAxMB1–x(bipy)3](PF6)2 have relative concentrations of the constituent complexes that are markedly different from the relative concentrations of the complexes initially present in the crystallizing solution. For example, when the nickel and iron complexes are co-crystallized from a solution containing a 50:50 ratio of each, the result is the formation of some crystals with a higher proportion of iron and others with a higher proportion of nickel. The relative concentrations of the metal complexes in the crystals can vary from those in the crystallizing solutions by as much as 15%. This result was observed for a range of combinations of metal complexes (Ni/Fe, Ni/Ru, and Fe/Ru) and a range of starting concentrations in the crystallizing solutions (90:10 through to 10:90 in 10% increments). To explain this remarkable result, we introduce the concept of “supramolecular selection”, which is a process driven by molecular recognition that leads to the partially selective aggregation of like molecules during crystallization.

Short answer versus multiple choice examination questions for first year chemistry

Multiple choice (MC) examinations are frequently used for the summative assessment of large classes because of their ease of marking and their perceived objectivity. However, traditional MC formats usually lead to a surface approach to learning, and do not allow students to demonstrate the depth of their knowledge or understanding. For these reasons, we have trialled the incorporation of short answer (SA) questions into the final examination of two first year chemistry units, alongside MC questions. Students’ overall marks were expected to improve, because they were able to obtain partial marks for the SA questions. Although large differences in some individual students’ performance in the two sections of their examinations were observed, most students received a similar percentage mark for their MC as for their SA sections and the overall mean scores were unchanged. In-depth analysis of all responses to a specific question, which was used previously as a MC question and in a subsequent semester in SA format, indicates that the SA format can have weaknesses due to marking inconsistencies that are absent for MC questions. However, inclusion of SA questions improved student scores on the MC section in one examination, indicating that their inclusion may lead to different study habits and deeper learning. We conclude that questions asked in SA format must be carefully chosen in order to optimise the use of marking resources, both financial and human, and questions asked in MC format should be very carefully checked by people trained in writing MC questions. These results, in conjunction with an analysis of the different examination formats used in first year chemistry units, have shaped a recommendation on how to reliably and cost-effectively assess first year chemistry, while encouraging higher order learning outcomes.

The Chemistry Discipline Network: One Year On

The Chemistry Discipline Network was funded in mid-2011, with the aim of improving communication between chemistry academics in Australia. In our first year of operation, we have grown to over 100 members, established a web presence, and produced substantial mapping reports on chemistry teaching in Australia. We are now working on the definition of standards for a chemistry degree based on the Threshold Learning Outcomes published by the Learning and Teaching Academic Standards Project.

Ruthenium(II) dichloro or dithiocyanato complexes with 4,4′:2′,2″:4″,4‴-quaterpyridinium ligands : towards photosensitisers with enhanced low-energy absorption properties

Fourteen new complexes of the form cis-\[RuIIX2(R2qpy2+)2]4+ (R2qpy2+ = a 4,4′:2′,2″:4″,4‴-quaterpyridinium ligand, X = Cl− or NCS−) have been prepared and isolated as their PF6− salts. Characterisation involved various techniques including 1H NMR spectroscopy and +electrospray or MALDI mass spectrometry. The UV–Vis spectra display intense intraligand π → π∗ absorptions, and also metal-to-ligand charge-transfer (MLCT) bands with two resolved maxima in the visible region. Red-shifts in the MLCT bands occur as the electron-withdrawing strength of the pyridinium groups increases, while replacing Cl− with NCS− causes blue-shifts. Cyclic voltammograms show quasi-reversible or reversible RuIII/II oxidation waves, and several ligand-based reductions that are irreversible. The variations in the redox potentials correlate with changes in the MLCT energies. A single-crystal X-ray structure has been obtained for a protonated form of a proligand salt, \[(4-(CO2H)Ph)2qpyH3+]\[HSO4]3·3H2O. Time-dependent density functional theory calculations give adequate correlations with the experimental UV–Vis spectra for the two carboxylic acid-functionalised complexes in DMSO. Despite their attractive electronic absorption spectra, these dyes are relatively inefficient photosensitisers on electrodes coated with TiO2 or ZnO. These observations are attributed primarily to weak electronic coupling with the surfaces, since the DFT-derived LUMOs include no electron density near the carboxylic acid anchors.

Embedding environmental sustainability in the undergraduate chemistry curriculum : a case study

In spite of increasing attention devoted to the importance of embedding sustainability in university curricula, few Australian universities include specific green chemistry units, and there is no mention of green or sustainable chemistry concepts in the majority of units. In this paper, an argument is posited that all universities should embed sustainable chemistry within all Chemistry courses because it is the morally correct stance to minimise the harm of climate change. Attitudes of chemistry lecturers towards integrating sustainability into their teaching have been probed and it was found, using an established model, that personal environmental perspectives are critical to their attitude. Importantly, academic staff whose research has an environmental component were more likely to incorporate sustainability into their teaching while others struggled to find ways to do so even when they believed it to be important. This paper will recommend that resources are required to assist academic staff without a green chemistry research program to incorporate sustainability into their teaching and several suggestions are provided.

The AusD Study: A population-based study of the determinants of serum 25-hydroxyvitamin D concentration across a broad latitude range

Observational studies suggest that people with a high serum 25-hydroxyvitamin D (25(OH)D) concentration may have reduced risk of chronic diseases such as osteoporosis, multiple sclerosis, type 1 diabetes, cardiovascular disease, and some cancers. The AusD Study (A Quantitative Assessment of Solar UV Exposure for Vitamin D Synthesis in Australian Adults) was conducted to clarify the relationships between ultraviolet (UV) radiation exposure, dietary intake of vitamin D, and serum 25(OH)D concentration among Australian adults residing in Townsville (19.3°S), Brisbane (27.5°S), Canberra (35.3°S), and Hobart (42.8°S). Participants aged 18-75 years were recruited from the Australian Electoral Roll between 2009 and 2010. Measurements were made of height, weight, waist:hip ratio, skin, hair, and eye color, blood pressure, and grip strength. Participants completed a questionnaire on sun exposure and vitamin D intake, together with 10 days of personal UV dosimetry and an associated sun-exposure and physical-activity diary that was temporally linked to a blood test for measurement of 25(OH)D concentration. Ambient solar UV radiation was also monitored at all study sites. We collected comprehensive, high-quality data from 1,002 participants (459 males, 543 females) assessed simultaneously across a range of latitudes and through all seasons. Here we describe the scientific and methodological issues considered in designing the AusD Study.

Using formative feedback to identify and support first year chemistry students with missing or misconceptions. A Practice Report

Students entering tertiary studies possess a diverse range of prior experiences in their academic preparation for tertiary chemistry so academics need tools to enable them to respond to issues in diversity in conceptual models possessed by entering students. Concept inventories can be used to provide formative feedback to help students identify concepts that they need to address to improve construction of subsequent understanding enabling their learning. Modular, formative learning activities that can be administered inside or outside of class in first year chemistry courses have been developed. These activities address key missing and mis-conceptions possessed by incoming student. Engagement in these learning activities by students and academics will help shift the culture of diagnostic and formative assessment within the tertiary context and address issues around the secondary/tertiary transition. This diagnostic/intervention framework is currently being trialed across five Australian tertiary institutions encompassing a large heterogeneous sample of students.

Outcomes of the Chemistry Discipline Network Mapping Exercises: Are the Threshold Learning Outcomes met?

The Chemistry Discipline Network has recently completed two distinct mapping exercises. The first is a snapshot of chemistry taught at 12 institutions around Australia in 2011. There were many similarities but also important differences in the content taught and assessed at different institutions. There were also significant differences in delivery, particularly laboratory contact hours, as well as forms and weightings of assessment. The second mapping exercise mapped the chemistry degrees at three institutions to the Threshold Learning Outcomes for chemistry. Importantly, some of the TLOs were addressed by multiple units at all institutions, while others were not met, or were met at an introductory level only. The exercise also exposed some challenges in using the TLOs as currently written.

Use of an on-line student response system : an analysis of adoption and continuance

The goal of this project was to initiate the use of an internet-based student response system in a large, first year chemistry class at a typical Australian university, and to verify its popularity and utility. A secondary goal was to influence other academic staff to adopt the system, initiating change at the discipline and Faculty level. The first goal was achieved with a high response rate using a commercial on-line system; however, the number of students engaging with the system dropped gradually during each class and over the course of the semester. Factors affecting student and staff adoption and continuance with technology are explored using established models.

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.