Proton-transfer versus nontransfer in compounds of the diazo-dye precursor 4-(phenyldiazenyl) aniline (aniline yellow) with strong organic acids: the 5-sulfosalicylate and the dichroic benzenesulfonate salts, and the 1:2 adduct with 3,5-dinitrobenzoic

The structures of two 1:1 proton-transfer red-black dye compounds formed by reaction of aniline yellow [4-(phenyldiazenyl)aniline] with 5-sulfosalicylic acid and benzenesulfonic acid, and a 1:2 nontransfer adduct compound with 3,5-dinitrobenzoic acid have been determined at either 130 or 200 K. The compounds are 2-(4-aminophenyl)-1-phenylhydrazin-1-ium 3-carboxy-4-hydroxybenzenesulfonate methanol solvate, C12H12N3+.C7H5O6S-.CH3OH (I), 2-(4-aminophenyl)-1-hydrazin-1-ium 4-(phenydiazinyl)anilinium bis(benzenesulfonate), 2C12H12N3+.2C6H5O3S-, (II) and 4-(phenyldiazenyl)aniline-3,5-dinitrobenzoic acid (1/2) C12H11N3.2C~7~H~4~N~2~O~6~, (III). In compound (I) the diaxenyl rather than the aniline group of aniline yellow is protonated and this group subsequently akes part in a primary hydrogen-bonding interaction with a sulfonate O-atom acceptor, producing overall a three-dimensional framework structure. A feature of the hydrogen bonding in (I) is a peripheral edge-on cation-anion association involving aromatic C--H...O hydrogen bonds, giving a conjoint R1/2(6)R1/2(7)R2/1(4)motif. In the dichroic crystals of (II), one of the two aniline yellow species in the asymmetric unit is diazenyl-group protonated while in the other the aniline group is protonated. Both of these groups form hydrogen bonds with sulfonate O-atom acceptors and thee, together with other associations give a one-dimensional chain structure. In compound (III), rather than proton-transfer, there is a preferential formation of a classic R2/2(8) cyclic head-to-head hydrogen-bonded carboxylic acid homodimer between the two 3,5-dinitrobenzoic acid molecules, which in association with the aniline yellow molecule that is disordered across a crystallographic inversion centre, result in an overall two-dimensional ribbon structure. This work has shown the correlation between structure and observed colour in crystalline aniline yellow compounds, illustrated graphically in the dichroic benzenesulfonate compound.

Maternal age and paternal age are associated with distinct childhood behavioural outcomes in a general population birth cohort

Abstract Background Recent studies show that advanced paternal age (APA) is associated with an increased risk of neurodevelopmental disorders such as autism, bipolar disorder and schizophrenia. A body of evidence also suggests that individuals who develop schizophrenia show subtle deviations in a range of behavioural domains during their childhood. The aim of the study was to examine the relationship between paternal and maternal ages and selected behavioural measures in children using a large birth cohort. Method Participants were singleton children (n = 21,753) drawn from the US Collaborative Perinatal Project. The outcome measures were assessed at 7 years. The main analyses examined the relationship between parental age and behavioural measures when adjusted for a range of potentially confounding variables, including age of the other parent, maternal race, socio-economic measures, sex, gestation length, maternal marital status, parental mental illness, and child's age-at-testing. Results Advanced paternal age was associated with a significantly increased risk of adverse ‘externalizing’ behaviours at age seven years. For every five year increase in paternal age, the odds of higher ‘externalizing’ behaviours was increased by 12% (OR = 1.12; 95% CI = 1.03, 1.21, p < 0.0001). The relationship persisted after adjusting for potential confounding factors. ‘Internalizing’ behavioural outcome was not associated with advanced paternal age. In contrast, advanced maternal age was significantly protective against adverse ‘externalizing’ behavioural outcomes, but associated with an increased risk of adverse ‘internalizing’ behavioural outcomes. Discussion The offspring of older fathers show a distinctly different pattern of behaviours compared to the offspring of older mothers. The diverse socio-cultural and biologically-mediated factors that underpin these findings remain to be clarified. In light of secular trends related to delayed parenthood, the mechanisms underlying these findings warrant closer scrutiny.

Challenges faced by general practitioners and allied mental health services in providing mental health services in rural Queensland

Objective: To examine the views of rural practitioners concerning issues and challenges in mental health service delivery and possible solutions. Design: A qualitative study using individual semi-structured interviews. Setting: Eight general practices from eight rural Queensland towns, three rural mental health services and two non-government organisations, with interviews being conducted before recent changes in government-subsidised access to allied health practitioners. Participants: A sample of 37 GPs, 19 Queensland Health mental health staff and 18 participants from community organisations. Main outcome measures: Analysis of qualitative themes from questions about the key mental health issues facing the town, bow they might be addressed and what challenges would be faced in addressing them. Results: There was substantial consensus that there are significant problems with inter-service communication and liaison, and that improved collaboration and shared care will form a critical part of any effective solution. Differences between groups reflected differing organisational contexts and priorities, and limitations to the understanding each had of the challenges that other groups were facing. C onclusions: Improvements to mental health staffing and to access to allied health might increase the ability of GPs to meet the needs of less complex patients, but specific strategies to promote better integrated services are required to address the needs of rural and regional patients with complex mental health problems. The current study provides a baseline against which effects of recent initiatives to improve mental health care can be assessed.

Bringing the internet down to earth : emerging spaces of locative media

Web 1.0 referred to the early, read-only internet; Web 2.0 refers to the ‘read-write web’ in which users actively contribute to as well as consume online content; Web 3.0 is now being used to refer to the convergence of mobile and Web 2.0 technologies and applications. One of the most important developments in mobile 3.0 is geography: with many mobile phones now equipped with GPS, mobiles promise to “bring the internet down to earth” through geographically-aware, or locative media. The internet was earlier heralded as “the death of geography” with predictions that with anyone able to access information from anywhere, geography would no longer matter. But mobiles are disproving this. GPS allows the location of the user to be pinpointed, and the mobile internet allows the user to access locally-relevant information, or to upload content which is geotagged to the specific location. It also allows locally-specific content to be sent to the user when the user enters a specific space. Location-based services are one of the fastest-growing segments of the mobile internet market: the 2008 AIMIA report indicates that user access of local maps increased by 347% over the previous 12 months, and restaurant guides/reviews increased by 174%. The central tenet of cultural geography is that places are culturally-constructed, comprised of the physical space itself, culturally-inflected perceptions of that space, and people’s experiences of the space (LeFebvre 1991). This paper takes a cultural geographical approach to locative media, anatomising the various spaces which have emerged through locative media, or “the geoweb” (Lake 2004). The geoweb is such a new concept that to date, critical discourse has treated it as a somewhat homogenous spatial formation. In order to counter this, and in order to demonstrate the dynamic complexity of the emerging spaces of the geoweb, the paper provides a topography of different types of locative media space: including the personal/aesthetic in which individual users geotag specific physical sites with their own content and meanings; the commercial, like the billboards which speak to individuals as they pass in Minority Report; and the social, in which one’s location is defined by the proximity of friends rather than by geography.

Does chemometrics enhance the performance of electroanalysis?

This review explores the question whether chemometrics methods enhance the performance of electroanalytical methods. Electroanalysis has long benefited from the well-established techniques such as potentiometric titrations, polarography and voltammetry, and the more novel ones such as electronic tongues and noses, which have enlarged the scope of applications. The electroanalytical methods have been improved with the application of chemometrics for simultaneous quantitative prediction of analytes or qualitative resolution of complex overlapping responses. Typical methods include partial least squares (PLS), artificial neural networks (ANNs), and multiple curve resolution methods (MCR-ALS, N-PLS and PARAFAC). This review aims to provide the practising analyst with a broad guide to electroanalytical applications supported by chemometrics. In this context, after a general consideration of the use of a number of electroanalytical techniques with the aid of chemometrics methods, several overviews follow with each one focusing on an important field of application such as food, pharmaceuticals, pesticides and the environment. The growth of chemometrics in conjunction with electronic tongue and nose sensors is highlighted, and this is followed by an overview of the use of chemometrics for the resolution of complicated profiles for qualitative identification of analytes, especially with the use of the MCR-ALS methodology. Finally, the performance of electroanalytical methods is compared with that of some spectrophotometric procedures on the basis of figures-of-merit. This showed that electroanalytical methods can perform as well as the spectrophotometric ones. PLS-1 appears to be the method of practical choice if the %relative prediction error of not, vert, similar±10% is acceptable.

Diagnosing postpartum depression in mothers and fathers : Whatever happened to anxiety?

Although anxiety disorders are documented in the literature for new mothers (but less so for fathers), rates of postpartum caseness tend to include only those with depression when diagnostic interviews or self-report measures validated on such interviews are used. This methodology therefore underestimates the true percentage of women and men who experience significant psychological difficulties postpartum. This has implications for assessment, treatment and screening for postnatal mood disorders. Two studies were conducted on a total of 408 women and 356 men expecting their first child. They were recruited antenatally, and interviewed at 6 weeks postpartum using the Diagnostic Interview Schedule. DSM-IV criteria were applied to determine the presence since birth of depression (major or minor), panic disorder, acute adjustment disorder with anxiety (meeting the criteria for generalised anxiety disorder except for the duration criterion), and phobia. The inclusion of diagnostic assessment for panic disorder and acute adjustment disorder with anxiety increased the rates of caseness by between 57 and 100% for mothers, and 31-130% for fathers, over the rates for major or minor depression. Inclusion of assessment for phobia further increased the rates of disorder in both samples.

Social adaptation of children with mild intellectual disability : effects of partial integration within primary school classes

Examined the social adaptation of 32 children in grades 3–6 with mild intellectual disability: 13 Ss were partially integrated into regular primary school classes and 19 Ss were full-time in separate classes. Sociometric status was assessed using best friend and play rating measures. Consistent with previous research, children with intellectual disability were less socially accepted than were a matched group of 32 children with no learning disabilities. Children in partially integrated classes received more play nominations than those in separate classes, but had no greater acceptance as a best friend. On teachers' reports, disabled children had higher levels of inappropriate social behaviours, but there was no significant difference in appropriate behaviours. Self-assessments by integrated children were more negative than those by children in separate classes, and their peer-relationship satisfaction was lower. Ratings by disabled children of their satisfaction with peer relationships were associated with ratings of appropriate social skills by themselves and their teachers, and with self-ratings of negative behaviour. The study confirmed that partial integration can have negative consequences for children with an intellectual disability.

Cost effectiveness of antimicrobial catheters in the intensive care unit : Addressing uncertainty in the decision

Introduction: Some types of antimicrobial-coated central venous catheters (A-CVC) have been shown to be cost-effective in preventing catheter-related bloodstream infection (CR-BSI). However, not all types have been evaluated, and there are concerns over the quality and usefulness of these earlier studies. There is uncertainty amongst clinicians over which, if any, antimicrobial-coated central venous catheters to use. We re-evaluated the cost-effectiveness of all commercially available antimicrobialcoated central venous catheters for prevention of catheter-related bloodstream infection in adult intensive care unit (ICU) patients. Methods: We used a Markov decision model to compare the cost-effectiveness of antimicrobial-coated central venous catheters relative to uncoated catheters. Four catheter types were evaluated; minocycline and rifampicin (MR)-coated catheters; silver, platinum and carbon (SPC)-impregnated catheters; and two chlorhexidine and silver sulfadiazine-coated catheters, one coated on the external surface (CH/SSD (ext)) and the other coated on both surfaces (CH/SSD (int/ext)). The incremental cost per qualityadjusted life-year gained and the expected net monetary benefits were estimated for each. Uncertainty arising from data estimates, data quality and heterogeneity was explored in sensitivity analyses. Results: The baseline analysis, with no consideration of uncertainty, indicated all four types of antimicrobial-coated central venous catheters were cost-saving relative to uncoated catheters. Minocycline and rifampicin-coated catheters prevented 15 infections per 1,000 catheters and generated the greatest health benefits, 1.6 quality-adjusted life-years, and cost-savings, AUD $130,289. After considering uncertainty in the current evidence, the minocycline and rifampicin-coated catheters returned the highest incremental monetary net benefits of $948 per catheter; but there was a 62% probability of error in this conclusion. Although the minocycline and rifampicin-coated catheters had the highest monetary net benefits across multiple scenarios, the decision was always associated with high uncertainty. Conclusions: Current evidence suggests that the cost-effectiveness of using antimicrobial-coated central venous catheters within the ICU is highly uncertain. Policies to prevent catheter-related bloodstream infection amongst ICU patients should consider the cost-effectiveness of competing interventions in the light of this uncertainty. Decision makers would do well to consider the current gaps in knowledge and the complexity of producing good quality evidence in this area.

Searching the self in Seoul : trans-youth and urban social networking in Korea

This paper presents a brief analysis of Seoul trans-youth’s search for identity through urban social networking, arguing that technological, socio-cultural and environmental (urban) contexts frame how mobility and ubiquity are (re)created in Seoul. The paper is empirically based on fieldwork conducted in Seoul, South Korea, from 2007 to 2008 as part of a research project on the mobile play culture of Seoul trans-youth(a term that will be explained in detail in the following section). Shared Visual Ethnography (SVE) was used as the research method which involved sharing of visual ethnographic data that were created by the participants. More specifically, the participants were asked to take photos, which were then shared and discussed with other participants and the researcher on the photo-sharing service Flickr. The research also involved a questionnaire and daily activity diaries, as well as interviews. A total of 44 Korean transyouths – including 23 females and 21 males – participated in interviews and photo-sharing. The paper draws specifically on the qualitative data from individual and/or group interviews, the total duration of which was 2–2.5 hours for each participant.

On the (partially) inalienable rights of participants in virtual communities

As virtual communities become more central to the everyday activities of connected individuals, we face increasingly pressing questions about the proper allocation of power, rights and responsibilities. This paper argues that our current legal discourse is ill-equipped to provide answers that will safeguard the legitimate interests of participants and simultaneously refrain from limiting the future innovative development of these spaces. From social networking sites like Facebook to virtual worlds like World of Warcraft and Second Life, participants who are banned from these communities stand to lose their virtual property, their connections to their friends and family, and their personal expression. Because our legal system views the proprietor’s interests as absolute private property rights, however, participants who are arbitrarily, capriciously or maliciously ejected have little recourse under law. This paper argues that, rather than assuming that a private property and freedom of contract model will provide the most desirable outcomes, a more critical approach is warranted. By rejecting the false dichotomy between ‘public’ and ‘private’ spaces, and recognising some of the absolutist and necessitarian trends in the current property debate, we may be able to craft legal rules that respect the social bonds between participants while simultaneously protecting the interests of developers.

Developing a quick and practical screen to improve the identification of poor hydration in geriatric and rehabilitative care

Dehydration has been associated with increased morbidity and mortality. Dehydration risk increases with advancing age, and will progressively become an issue as the aging population increases. Worldwide, those aged 60 years and over are the fastest growing segment of the population. The study aimed to develop a clinically practical means to identify dehydration amongst older people in the clinical care setting. Older people aged 60 years or over admitted to the Geriatric and Rehabilitation Unit (GARU) of two tertiary teaching hospitals were eligible for participation in the study. Ninety potential screening questions and 38 clinical parameters were initially tested on a single sample (n=33) with the most promising 11 parameters selected to undergo further testing in an independent group (n=86). Of the almost 130 variables explored, tongue dryness was most strongly associated with poor hydration status, demonstrating 64% sensitivity and 62% specificity within the study participants. The result was not confounded by age, gender or body mass index. With minimal training, inter-rater repeatability was over 90%. This study identified tongue dryness as a potentially practical tool to identify dehydration risk amongst older people in the clinical care setting. Further studies to validate the potential screen in larger and varied populations of older people are required

Setting hospital infection control policy : a decision-making framework incorporating health economics and healthcare epidemiology

Background: Reducing rates of healthcare acquired infection has been identified by the Australian Commission on Safety and Quality in Health Care as a national priority. One of the goals is the prevention of central venous catheter-related bloodstream infection (CR-BSI). At least 3,500 cases of CR-BSI occur annually in Australian hospitals, resulting in unnecessary deaths and costs to the healthcare system between $25.7 and $95.3 million. Two approaches to preventing these infections have been proposed: use of antimicrobial catheters (A-CVCs); or a catheter care and management ‘bundle’. Given finite healthcare budgets, decisions about the optimal infection control policy require consideration of the effectiveness and value for money of each approach. Objectives: The aim of this research is to use a rational economic framework to inform efficient infection control policy relating to the prevention of CR-BSI in the intensive care unit. It addresses three questions relating to decision-making in this area: 1. Is additional investment in activities aimed at preventing CR-BSI an efficient use of healthcare resources? 2. What is the optimal infection control strategy from amongst the two major approaches that have been proposed to prevent CR-BSI? 3. What uncertainty is there in this decision and can a research agenda to improve decision-making in this area be identified? Methods: A decision analytic model-based economic evaluation was undertaken to identify an efficient approach to preventing CR-BSI in Queensland Health intensive care units. A Markov model was developed in conjunction with a panel of clinical experts which described the epidemiology and prognosis of CR-BSI. The model was parameterised using data systematically identified from the published literature and extracted from routine databases. The quality of data used in the model and its validity to clinical experts and sensitivity to modelling assumptions was assessed. Two separate economic evaluations were conducted. The first evaluation compared all commercially available A-CVCs alongside uncoated catheters to identify which was cost-effective for routine use. The uncertainty in this decision was estimated along with the value of collecting further information to inform the decision. The second evaluation compared the use of A-CVCs to a catheter care bundle. We were unable to estimate the cost of the bundle because it is unclear what the full resource requirements are for its implementation, and what the value of these would be in an Australian context. As such we undertook a threshold analysis to identify the cost and effectiveness thresholds at which a hypothetical bundle would dominate the use of A-CVCs under various clinical scenarios. Results: In the first evaluation of A-CVCs, the findings from the baseline analysis, in which uncertainty is not considered, show that the use of any of the four A-CVCs will result in health gains accompanied by cost-savings. The MR catheters dominate the baseline analysis generating 1.64 QALYs and cost-savings of $130,289 per 1.000 catheters. With uncertainty, and based on current information, the MR catheters remain the optimal decision and return the highest average net monetary benefits ($948 per catheter) relative to all other catheter types. This conclusion was robust to all scenarios tested, however, the probability of error in this conclusion is high, 62% in the baseline scenario. Using a value of $40,000 per QALY, the expected value of perfect information associated with this decision is $7.3 million. An analysis of the expected value of perfect information for individual parameters suggests that it may be worthwhile for future research to focus on providing better estimates of the mortality attributable to CR-BSI and the effectiveness of both SPC and CH/SSD (int/ext) catheters. In the second evaluation of the catheter care bundle relative to A-CVCs, the results which do not consider uncertainty indicate that a bundle must achieve a relative risk of CR-BSI of at least 0.45 to be cost-effective relative to MR catheters. If the bundle can reduce rates of infection from 2.5% to effectively zero, it is cost-effective relative to MR catheters if national implementation costs are less than $2.6 million ($56,610 per ICU). If the bundle can achieve a relative risk of 0.34 (comparable to that reported in the literature) it is cost-effective, relative to MR catheters, if costs over an 18 month period are below $613,795 nationally ($13,343 per ICU). Once uncertainty in the decision is considered, the cost threshold for the bundle increases to $2.2 million. Therefore, if each of the 46 Level III ICUs could implement an 18 month catheter care bundle for less than $47,826 each, this approach would be cost effective relative to A-CVCs. However, the uncertainty is substantial and the probability of error in concluding that the bundle is the cost-effective approach at a cost of $2.2 million is 89%. Conclusions: This work highlights that infection control to prevent CR-BSI is an efficient use of healthcare resources in the Australian context. If there is no further investment in infection control, an opportunity cost is incurred, which is the potential for a more efficient healthcare system. Minocycline/rifampicin catheters are the optimal choice of antimicrobial catheter for routine use in Australian Level III ICUs, however, if a catheter care bundle implemented in Australia was as effective as those used in the large studies in the United States it would be preferred over the catheters if it was able to be implemented for less than $47,826 per Level III ICU. Uncertainty is very high in this decision and arises from multiple sources. There are likely greater costs to this uncertainty for A-CVCs, which may carry hidden costs, than there are for a catheter care bundle, which is more likely to provide indirect benefits to clinical practice and patient safety. Research into the mortality attributable to CR-BSI, the effectiveness of SPC and CH/SSD (int/ext) catheters and the cost and effectiveness of a catheter care bundle in Australia should be prioritised to reduce uncertainty in this decision. This thesis provides the economic evidence to inform one area of infection control, but there are many other infection control decisions for which information about the cost-effectiveness of competing interventions does not exist. This work highlights some of the challenges and benefits to generating and using economic evidence for infection control decision-making and provides support for commissioning more research into the cost-effectiveness of infection control.

Asymmetrical DC link voltage configuration for a diode-clamped inverter

There is a trade off between a number of output voltage levels and the reliability and efficiency of a multilevel converter. A new configuration of diode-clamped multilevel inverters with a different combination of DC link capacitors voltage has been proposed in this paper. Two different symmetrical and asymmetrical unequal arrangements for a four-level diode-clamped inverter have been compared, in order to find an optimum arrangement with lower switching losses and optimised output voltage quality. The simulation and hardware results for a four-level inverter show that the asymmetrical configuration can obtain more output voltage levels with the same number of components compared with a conventional four-level inverter and this will lead to the reduction of the harmonic content of the output voltage. A new family of multi-output DC-DC converters with a simple control strategy has been utilised as a front-end converter to supply the DC link capacitor voltages for the optimised configuration.