Desorption electrospray ionisation mass spectrometry reveals in situ modification of a hindered amine light stabiliser resulting from direct N–OR bond cleavage

Detection and characterisation of structural modifications of a hindered amine light stabiliser (HALS) directly from a polyester-based coil coating have been achieved by desorption electrospray ionisation mass spectrometry (DESI-MS) for the first time. In situ detection is made possible by exposing the coating to an acetone vapour atmosphere prior to analysis. This is a gentle and non-destructive treatment that allows diffusion of analyte to the surface without promoting lateral migration. Using this approach a major structural modification of the HALS TINUVIN®123 (bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate) was discovered where one N-ether piperidine moiety (N-OC8H17) is converted to a secondary piperidine (N–H). With the use of 2-dimensional DESI-MS imaging the modification was observed to arise during high curing temperatures (ca. 260 °C) and under simulated physiological conditions (80 °C, full solar spectrum). It is proposed that the secondary piperidine derivative is a result of a highly reactive aminyl radical intermediate produced by N–O homolytic bond cleavage. The nature of the bond cleavage is also suggested by ESR spin-trapping experiments employing α-phenyl-N-tert-butyl nitrone (PBN) in toluene at 80 °C. The presence of a secondary piperidine derivative in situ and the implication of N–OR competing with NO–R bond cleavage suggest an alternative pathway for generation of the nitroxyl radical—an essential requirement in anti-oxidant activity that has not previously been described for the N-ether sub-class of HALS.

Wasting Time? Art, Science and New Experience. Examining the Artwork, Know more (House of Commons)

Today the future is travelling rapidly towards us, shaped by all that which we have historically thrown into it. Much of what we have designed for our world over the ages, and much of what we continue to embrace in the pursuit of mainstream economic, cultural and social imperatives, embodies unacknowledged ‘time debts’. Every decision we make today has the potential to ‘give time to’, or take ‘time away’ from that future. This idea that ‘everything‘ inherently embodies ‘future time left’ is underlined by design futurist Tony Fry when he describes how we so often ‘waste’ or ‘take away’ ‘future time’. “In our endeavours to sustain ourselves in the short term we collectively act in destructive ways towards the very things we and all other beings fundamentally depend upon”

Why 'down under' is a cut above: a comparison of rates of and reasons for caesarean section in England and Australia

Background Most studies examining determinants of rising rates of caesarean section have examined patterns in documented reasons for caesarean over time in a single location. Further insights could be gleaned from cross-cultural research that examines practice patterns in locations with disparate rates of caesarean section at a single time point. Methods We compared both rates of and main reason for pre-labour and intrapartum caesarean between England and Queensland, Australia, using data from retrospective cross-sectional surveys of women who had recently given birth in England (n = 5,250) and Queensland (n = 3,467). Results Women in Queensland were more likely to have had a caesarean birth (36.2%) than women in England (25.1% of births; OR = 1.44, 95% CI = 1.28-1.61), after adjustment for obstetric characteristics. Between-country differences were found for rates of pre-labour caesarean (21.2% vs. 12.2%) but not for intrapartum caesarean or assisted vaginal birth. Compared to women in England, women in Queensland with a history of caesarean were more likely to have had a pre-labour caesarean and more likely to have had an intrapartum caesarean, due only to a previous caesarean. Among women with no previous caesarean, Queensland women were more likely than women in England to have had a caesarean due to suspected disproportion and failure to progress in labour. Conclusions The higher rates of caesarean birth in Queensland are largely attributable to higher rates of caesarean for women with a previous caesarean, and for the main reason of having had a previous caesarean. Variation between countries may be accounted for by the absence of a single, comprehensive clinical guideline for caesarean section in Queensland. Keywords: Caesarean section; Childbirth; Pregnancy; Cross-cultural comparison; Vaginal birth after caesarean; Previous caesarean section; Patient-reported data; Quality improvement

Assessing physical activity during youth sport : the observational system for recording activity in children : youth sports (OSRAC:YS)

The purpose of this study was to evaluate the validity and inter-rater reliability of the Observation System for Recording Activity in Children: Youth Sports (OSRAC:YS). Children (N=29) participating in a parks and recreation soccer program were observed during regularly scheduled practices. Physical activity (PA) intensity and contextual factors were recorded by momentary time-sampling procedures (10-sec observe, 20-sec record). Two observers simultaneously observed and recorded children's PA intensity, practice context, social context, coach behavior, and coach proximity. Inter-rater reliability was based on agreement (Kappa) between the observer's coding for each category, and the Intraclass Correlation Coefficient (ICC) for percent of time spent in MVPA. Validity was assessed by calculating the correlation between OSRAC:YS estimated and objectively measured MVPA. Kappa statistics for each category demonstrated substantial to almost perfect inter-observer agreement (Κappa = 0.67 to 0.93). The ICC for percent time in MVPA was 0.76 (95% C.I. = 0.49 - 0.90). A significant correlation (r = 0.73) was observed for MVPA recorded by observation and MVPA measured via accelerometry. The results indicate the OSRAC:YS is a reliable and valid tool for measuring children's PA and contextual factors during a youth soccer practice.

The application of luminance mapping to discomfort glare : a modified glare index for green buildings

Unfortunately, there is no reliable method to adequately quantify discomfort glare. One of the world's largest investigations on discomfort glare was conducted in five Green Star office buildings in Brisbane. Luminance mapping via high dynamic range images and Post Occupancy Evaluation surveys were used in the data collection. A new glare index, termed the Unified Glare Probability, was developed to predict discomfort glare within these types of office buildings.

Suppression of cluster ions during particle formation events in the atmosphere

Cluster ions and charged and neutral nanoparticle concentrations were monitored using a neutral cluster and air ion spectrometer (NAIS) over a period of one year in Brisbane, Australia. The study yielded 242 complete days of usable data, of which particle formation events were observed on 101 days. Small, intermediate and large ion concentrations were evaluated in real time. In the diurnal cycle, small ion concentration was highest during the second half of the night while large ion concentrations were a maximum during the day. The small ion concentration showed a decrease when the large ion concentration increased. Particle formation was generally followed by a peak in the intermediate ion concentration. The rate of increase of intermediate ions was used as the criteria for identifying particle formation events. Such events were followed by a period of growth to larger sizes and usually occurred between 8 am and 2 pm. Particle formation events were found to be related to the wind direction. The gaseous precursors for the production of secondary particles in the urban environment of Brisbane have been shown to be ammonia and sulfuric acid. During these events, the nanoparticle number concentrations in the size range 1.6 to 42 nm, which were normally lower than 1x104 cm-3, often exceeded 5x104 cm-3 with occasional values over 1x105 cm-3. Cluster ions generally occurred in number concentrations between 300 and 600 cm-3 but decreased significantly to about 200 cm-3 during particle formation events. This was accompanied by an increase in the large ion concentration. We calculated the fraction of nanoparticles that were charged and investigated the occurrence of possible overcharging during particle formation events. Overcharging is defined as the condition where the charged fraction of particles is higher than in charge equilibrium. This can occur when cluster ions attach to neutral particles in the atmosphere, giving rise to larger concentrations of charged particles in the short term. Ion-induced nucleation is one of the mechanisms of particle formation in the atmosphere, and overcharging has previously been considered as an indicator of this process. The possible role of ions in particle formation was investigated.

Environmental productivity and Kuznets curve in India

As a result of India's extremely rapid economic growth, the scale and seriousness of environmental problems are no longer in doubt. Whether pollution abatement technologies are utilized more efficiently is crucial in the analysis of environmental management because it influences the cost of alternative production and pollution abatement technologies. In this study, we use state-level industry data of sulfur dioxide, nitrogen dioxide, and suspended particular matter over the period 1991-2003. Employing recently developed productivity measurement technique, we show that overall environmental productivities decrease over time in India. Furthermore, we analyze the determinants of environmental productivities and find environmental Kuznets curve type relationship existences between environmental productivity and income. Panel analysis results show that the scale effect dominates over the technique effect. Therefore, a combined effect of income on environmental productivity is negative.

A story about being engaged in research : buzzing bees, small business and Australian unfair dismissal laws

Protection for employees from unfair dismissal (UFD) has been around in Australia under various guises for 30 years or so (Chapman, 2006). Labour standards, and particularly ILO Convention 158 (Convention Concerning Termination of Employment at the Initiative of the Employer 1982), underpin the adoption of a particular form of federal statutory UFD regime which first appeared in the 1993 reforms to the Industrial Relations Act 1998 (Commonwealth). Its existence, however, has not been uncontroversial, and the meaning, operation, scope and remedies have attracted attention over time. In fact, the first reforms to the federal UFD regime were undertaken under the Keating Labor government three months after they were enacted (Chapman, ibid.). Further reforms were made by the incoming Howard Liberal-national coalition government through the Workplace Relations Act 1996 (Commonwealth) (WRA), and arguably these reforms continued down the ‘contraction’ path (ibid.).

An analytical framework for quantifying aquifer response time scales associated with transient boundary conditions

A major challenge in studying coupled groundwater and surface-water interactions arises from the considerable difference in the response time scales of groundwater and surface-water systems affected by external forcings. Although coupled models representing the interaction of groundwater and surface-water systems have been studied for over a century, most have focused on groundwater quantity or quality issues rather than response time. In this study, we present an analytical framework, based on the concept of mean action time (MAT), to estimate the time scale required for groundwater systems to respond to changes in surface-water conditions. MAT can be used to estimate the transient response time scale by analyzing the governing mathematical model. This framework does not require any form of transient solution (either numerical or analytical) to the governing equation, yet it provides a closed form mathematical relationship for the response time as a function of the aquifer geometry, boundary conditions, and flow parameters. Our analysis indicates that aquifer systems have three fundamental time scales: (i) a time scale that depends on the intrinsic properties of the aquifer; (ii) a time scale that depends on the intrinsic properties of the boundary condition, and; (iii) a time scale that depends on the properties of the entire system. We discuss two practical scenarios where MAT estimates provide useful insights and we test the MAT predictions using new laboratory-scale experimental data sets.

Kirsten ras mutations in patients with colorectal cancer : the ‘RASCAL II’ study

Researchers worldwide with information about the Kirsten ras (Ki-ras) tumour genotype and outcome of patients with colorectal cancer were invited to provide that data in a schematized format for inclusion in a collaborative database called RASCAL (The Kirsten ras in-colorectal-cancer collaborative group). Our results from 2721 such patients have been presented previously and for the first time in any common cancer, showed conclusively that different gene mutations have different impacts on outcome, even when the mutations occur at the same site on the genome. To explore the effect of Ki-ras mutations at different stages of colorectal cancer, more patients were recruited to the database, which was reanalysed when information on 4268 patients from 42 centres in 21 countries had been entered. After predetermined exclusion criteria were applied, data on 3439 patients were entered into a multivariate analysis. This found that of the 12 possible mutations on codons 12 and 13 of Kirsten ras, only one mutation on codon 12, glycine to valine, found in 8.6% of all patients, had a statistically significant impact on failure-free survival (P = 0.004, HR 1.3) and overall survival (P = 0.008, HR 1.29). This mutation appeared to have a greater impact on outcome in Dukes’ C cancers (failure-free survival, P = 0.008, HR 1.5; overall survival P = 0.02, HR 1.45) than in Dukes’ B tumours (failure-free survival, P = 0.46, HR 1.12; overall survival P = 0.36, HR 1.15). Ki-ras mutations may occur early in the development of pre-cancerous adenomas in the colon and rectum. However, this collaborative study suggests that not only is the presence of a codon 12 glycine to valine mutation important for cancer progression but also that it may predispose to more aggressive biological behaviour in patients with advanced colorectal cancer.

Stem-like cells with luminal progenitor phenotype survive castration in human prostate cancer

Castration is the standard therapy for advanced prostate cancer (PC). Although this treatment is initially effective, tumors invariably relapse as incurable, castration-resistant PC (CRPC). Adaptation of androgen-dependent PC cells to an androgen-depleted environment or selection of pre-existing,CRPC cells have been proposed as mechanisms of CRPC development. Stem cell (SC)-like PC cells have been implicated not only as tumor initiating/maintaining in PC but also as tumor-reinitiating cells in CRPC. Recently, castration-resistant cells expressing the NK3 homeobox 1 (Nkx3-1) (CARNs), the other luminal markers cytokeratin 18 (CK18) and androgen receptor (AR), and possessing SC properties, have been found in castrated mouse prostate and proposed as the cell-of-origin of CRPC. However, the human counterpart of CARNs has not been identified yet. Here, we demonstrate that in the human PC xenograft BM18, preexisting SC-like and neuroendocrine (NE) PC cells are selected by castration and survive as totally quiescent. SClike BM18 cells, displaying the SC markers aldehyde dehydrogenase 1A1 or NANOG, coexpress the luminal markers NKX3-1, CK18, and a low level of AR (ARlow) but not basal or NE markers. These CR luminal SC-like cells, but not NE cells, reinitiate BM18 tumor growth after androgen replacement. The ARlow seems to mediate directly both castration survival and tumor reinitiation. This study identifies for the first time in human PC SC-/CARN-like cells that may represent the cell-of-origin of tumor reinitiation as CRPC. This finding will be fundamental for refining the hierarchy among human PC cancer cells and may have important clinical implications.

Convergence in European corporate governance : the audit committee concept

This paper analyses recent corporate governance codes issued by 20 countries for evidence of convergence in corporate governance systems in Europe. The analysis shows that there has been a degree of convergence towards an Anglo-Saxon model of corporate governance as the audit committee concept is widely accepted in countries with both unitary and two-tier governance systems. Further, the latest audit committee recommendations in countries that have issued several governance codes show a strengthening of the recommendations for an audit committee over time in line with the Anglo-Saxon audit committee concept and convergence with the debate in the US and UK on issues such as the independence and financial expertise of members. However, consistent with the literature on the convergence of European corporate governance systems, at an operational level there is limited consistency in the recommended structure and role of audit committees.

Regulating Workplace Risks: A Comparative Study of Inspection Regimes in Times of Change

Regulating Workplace Risks is a study of regulatory inspection of occupational health and safety (OHS) and its management in five countries – Australia, Canada (Québec), France, Sweden and the UK – during a time of major change. It examines the implications of the shift from specification to process based regulation, in which attention has been increasingly directed to the means of managing OHS more systematically at a time in which a major restructuring of work has occurred in response to the globalised economy. These changes provide both the context and material for a wider discussion of the nature of regulation and regulatory inspection and their role in protecting the health, safety and well-being of workers in advanced market economies.

Exploring diarrhoea, enteral nutrition and intestinal microbial flora relationships in critically ill patients

Diarrhoea is a common complication observed in critically ill patients. Relationships between diarrhoea, enteral nutrition and aerobic intestinal microflora have been disconnectedly examined in this patient cohort. This research used a two-study, observational design to examine these associations. Higher diarrhoea incidence rates were observed when patients received enteral tube feeding, had abnormal serum blood results, received multiple medications and had aerobic microflora dysbiosis. Further, significant aerobic intestinal microflora changes were observed over time in patients who experienced diarrhoea. These results establish a platform for further work to improve the intestinal health of critically ill patients.

Evaluating the responsiveness of accelerometry to detect change in physical activity

The responsiveness to change of the Actical and ActiGraph accelerometers was assessed in children and adolescents. Participants (n=208) aged 6-16 years completed two simulated free-living protocols, one with primarily light-to-moderate physical activities (PA) and one with mostly moderate-to-vigorous PA. Time in sedentary, light, moderate, and vigorous PA was estimated using 8 previously developed cut-points (4 for Actical and 4 for ActiGraph) and 15-s and 30-s epochs. Accelerometer responsiveness for detecting differences in PA between protocols was assessed using standardized response means (SRM). SRM values >/=0.8 represented high responsiveness to change. Both accelerometers showed high responsiveness for all PA intensities (SRMs = 1.2-4.7 for Actical and 1.1-3.3 for ActiGraph). All cut-points and epoch lengths yielded high responsiveness, and choice of cut-points and epoch length had little effect on responsiveness. Thus, both the Actical and ActiGraph can detect change in PA in a simulated free-living setting, irrespective of cut-point selection or epoch length.