Size Isn't Everything: Geometric Tuning in Polycyclic Aromatic Hydrocarbons and Its Implications for Carbon Nanodots.

Recent developments in light-emitting carbon nanodots and molecular organic semiconductors have seen renewed interest in the properties of polycyclic aromatic hydrocarbons (PAHs) as a family. The networks of delocalized π electrons in sp2-hybridized carbon grant PAHs light-emissive properties right across the visible spectrum. However, the mechanistic understanding of their emission energy has been limited due to the ground state-focused methods of determination. This computational chemistry work, therefore, seeks to validate existing rules and elucidate new features and characteristics of PAHs that influence their emissions. Predictions based on (time-dependent) density functional theory account for the full 3-dimensional electronic structure of ground and excited states and reveal that twisting and near-degeneracies strongly influence emission spectra and may therefore be used to tune the color of PAHs and, hence, carbon nanodots. We particularly note that the influence of twisting goes beyond torsional destabilization of the ground-state and geometric relaxation of the excited state, with a third contribution associated with the electric transition dipole. Symmetries and peri-condensation may also have an effect, but this could not be statistically confirmed. In pursuing this goal, we demonstrate that with minimal changes to molecular size, the entire visible spectrum may be spanned by geometric modification alone; we have also provided a first estimate of emission energy for 35 molecules currently lacking published emission spectra as well as clear guidelines for when more sophisticated computational techniques are required to predict the properties of PAHs accurately.

New approaches narrow global species estimates for beetles, insects, and terrestrial arthropods.

It has been suggested that we do not know within an order of magnitude the number of all species on Earth [May RM (1988) Science 241(4872):1441-1449]. Roughly 1.5 million valid species of all organisms have been named and described [Costello MJ, Wilson S, Houlding B (2012) Syst Biol 61(5):871-883]. Given Kingdom Animalia numerically dominates this list and virtually all terrestrial vertebrates have been described, the question of how many terrestrial species exist is all but reduced to one of how many arthropod species there are. With beetles alone accounting for about 40% of all described arthropod species, the truly pertinent question is how many beetle species exist. Here we present four new and independent estimates of beetle species richness, which produce a mean estimate of 1.5 million beetle species. We argue that the surprisingly narrow range (0.9-2.1 million) of these four autonomous estimates--derived from host-specificity relationships, ratios with other taxa, plant:beetle ratios, and a completely novel body-size approach--represents a major advance in honing in on the richness of this most significant taxon, and is thus of considerable importance to the debate on how many species exist. Using analogous approaches, we also produce independent estimates for all insects, mean: 5.5 million species (range 2.6-7.8 million), and for terrestrial arthropods, mean: 6.8 million species (range 5.9-7.8 million), which suggest that estimates for the world's insects and their relatives are narrowing considerably.

Duration of participation in continuous quality improvement: a key factor explaining improved delivery of Type 2 diabetes services.

BACKGROUND: It is generally recognised that continuous quality improvement (CQI) programs support development of high quality primary health care systems. However, there is limited evidence demonstrating their system-wide effectiveness. We examined variation in quality of Type 2 diabetes service delivery in over 100 Aboriginal and Torres Strait Islander primary health care centres participating in a wide-scale CQI project over the past decade, and determined the influence of health centre and patient level factors on quality of care, with specific attention to health centre duration of participation in a CQI program. METHODS: We analysed over 10,000 clinical audit records to assess quality of Type 2 diabetes care of patients in 132 Aboriginal and Torres Strait Islander community health centres in five states/territories participating in the ABCD project for varying periods between 2005 and 2012. Process indicators of quality of care for each patient were calculated by determining the proportion of recommended guideline scheduled services that were documented as delivered. Multilevel regression models were used to quantify the amount of variation in Type 2 diabetes service delivery attributable to health centre or patient level factors and to identify those factors associated with greater adherence to best practice guidelines. RESULTS: Health centre factors that were independently associated with adherence to best practice guidelines included longer participation in the CQI program, remoteness of health centres, and regularity of client attendance. Significantly associated patient level variables included greater age, and number of co-morbidities and disease complications. Health centre factors explained 37% of the differences in level of service delivery between jurisdictions with patient factors explaining only a further 1%. CONCLUSIONS: At the health centre level, Type 2 diabetes service delivery could be improved through long term commitment to CQI, encouraging regular attendance (for example, through patient reminder systems) and improved recording and coordination of patient care in the complex service provider environments that are characteristic of non-remote areas.

Understanding and including 'pink-collar' workers in employment-based travel demand models.

The segmentation of commuters into either blue or white-collar workers remains is still common in urban transport models. Internationally, models have started to use more elaborate segmentations, more reflective of changes in labour markets, such as increased female participation. Finding appropriate labour market segmentations for commute trip modelling remains a challenge. This paper harnesses a data-driven approach using unsupervised clustering-applied to 2017-20 South East Queensland Travel Survey (SEQTS) data. Commuter types are grouped by occupational, industry, and socio-demographic variables (i.e., gender, age, household size, household vehicle ownership and worker skill score). The results show that at a large number of clusters (i.e., k = 8) a highly distinct set of commuter types can be observed. But model run times tend to require a much smaller number of market segments. When only three clusters are formed (k = 3) a market segmentation emerges with one female-dominated type ('pink collar'), one male-dominated type ('blue collar') and one with both genders almost equally involved ('white collar'). There are nuances as to which workers are included in each segment, and differences in travel behaviours across the three types. 'Pink collar' workers are mostly comprised of female clerical and administrative workers, community and personal service workers and sales workers. They have the shortest median commutes for both private motorised and active transport modes. The approach and methods should assist transport planners to derive more accurate and robust market segmentations for use in large urban transport models, and, better predict the value of alternative transport projects and policies for all types of commuters.

Occurrence and seasonal variations of algal toxins in water, phytoplankton and shellfish from North Stradbroke Island, Queensland, Australia.

A number of marine microalgae are known to produce toxins that can accumulate in shellfish and when eaten, lead to toxic and potentially fatal reactions in humans. This paper reports on the occurrence and seasonal variations of algal toxins in the waters, phytoplankton and shellfish of Southeast Queensland, Australia. These algal toxins include okadaic acid (OA), domoic acid (DA), gymnodimine (GD), pectenotoxin-2 (PTX-2) and pectenotoxin-2-seco acid (PTX-2-SA), which were detected in the sampled shellfish and phytoplankton, via HPLC-MS/MS. Dissolved OA, PTX-2 and GD were also detected in the samples collected from the water column. This was the first occasion that DA and GD have been reported in shellfish, phytoplankton and the water column in Queensland waters. Phytoplankton tows contained both the toxic Dinophysis and Pseudo-nitzschia algae species, and are suspected of being the most likely producers of the OA, PTX-2s and DA found in shellfish of this area. The number of cells, however, did not correlate with the amount of toxins present in either shellfish or phytoplankton. This indicates that toxin production by algae varies with time and the species present and that number of cells alone cannot be used as an indicator for the presence of toxins. The presence of OA and PTX-2s were more frequently seen in the summer, while DA and GD were detected throughout the year and without any obvious seasonal patterns.