Electrocatalytic oxidation of ascorbic acid using a single layer of gold nanoparticles immobilized on 1,6-hexanedithiol modified gold electrode

This paper describes the electrocatalytic oxidation of ascorbic acid (AA) in phosphate buffer solution by the immobilized citrate capped gold nanoparticles (AuNPs) on 1,6-hexanedithiol (HDT) modified Au electrode. X-ray photoelectron spectrum (XPS) of HDT suggests that it forms a monolayer on Au surface through one of the two single bondSH groups and the other single bondSH group is pointing away from the electrode surface. The free single bondSH groups of HDT were used to covalently attach colloidal AuNPs. The covalent attachment of AuNPs on HDT monolayer was confirmed from the observed characteristic carboxylate ion stretching modes of citrate attached with AuNPs in the infra-red reflection absorption spectrum (IRRAS) in addition to a higher reductive desorption charges obtained for AuNPs immobilized on HDT modified Au (Au/HDT/AuNPs) electrode in 0.1 M KOH when compared to HDT modified Au (Au/HDT) electrode. The electron transfer reaction of [Fe(CN)6]4−/3− was markedly hindered at the HDT modified Au (Au/HDT) electrode while it was restored with a peak separation of 74 mV after the immobilization of AuNPs on Au/HDT (Au/HDT/AuNPs) electrode indicating a good electronic communication between the immobilized AuNPs and the underlying bulk Au electrode through a HDT monolayer. The Cottrell slope obtained from the potential-step chronoamperometric measurements for the reduction of ferricyanide at Au/HDT/AuNPs was higher than that of bare Au electrode indicating the increased effective surface area of AuNPs modified electrode. The Au/HDT/AuNPs electrode exhibits excellent electrocatalytic activity towards the oxidation of ascorbic acid (AA) by enhancing the oxidation peak current to more than two times with a 210 mV negative shift in the oxidation potential when compared to a bare Au electrode. The standard heterogeneous electron transfer rate constant (ks) calculated for AA oxidation at Au/HDT/AuNPs electrode was 5.4 × 10−3 cm s−1. The oxidation peak of AA at Au/HDT/AuNPs electrode was highly stable upon repeated potential cycling. Linear calibration plot was obtained for AA over the concentration range of 1–110 μM with a correlation coefficient of 0.9950. The detection limit of AA was found to be 1 μM. The common physiological interferents such as glucose, oxalate ions and urea do not show any interference within the detection limit of AA. The selectivity of the AuNPs modified electrode was illustrated by the determination of AA in the presence of uric acid.

Building the safety case for UAS operations in support of natural disaster response

A framework supporting the systematic development of safety cases for Unmanned Aircraft System (UAS) operations in a broad range of civil and commercial applications is presented. The case study application is the use of UAS for disaster response. In those States where regulations do not preclude UAS operations altogether, approvals for UAS operations can be granted on a case-by-case basis contingent on the provision of a safety case acceptable to the relevant National Airworthiness Authority (NAA). A safety case for UAS operations must show how the risks associated with the hazards have been managed to an acceptable level. The foundational components necessary for structuring and assessing these safety cases have not yet been proposed. Barrier-bow-tie models are used in this paper to structure the safety case for the two primary hazards of 1) a ground impact, and 2) a Mid-Air Collision (MAC). The models establish the set of Risk Control Variables (RCVs) available to reduce the risk. For the ground-impact risk model, seven RCVs are identified which in combination govern the probability of an accident. Similarly, ten RCVs are identified within the MAC model. The effectiveness of the RCVs and how they can implemented in terms of processes, policies, devices, practices, or other actions for each of the case-study applications are discussed. The framework presented can provide for the more systematic and consistent regulation of UAS through a "safety target" approach.

Inhibition of form-deprivation myopia by a GABAAOr receptor antagonist, (1,2,5,6-tetrahydropyridin-4-yl) methylphosphinic acid (TPMPA), in guinea pigs

Purpose To investigate the effects of the relatively selective GABAAOr receptor antagonist (1,2,5,6-tetrahydropyridin-4-yl) methylphosphinic acid (TPMPA) on form-deprivation myopia (FDM) in guinea pigs. Methods A diffuser was applied monocularly to 30 guinea pigs from day 10 to 21. The animals were randomized to one of five treatment groups. The deprived eye received daily sub-conjunctival injections of 100 μl TPMPA at a concentration of (i) 0.03 %, ( ii) 0.3 %, or (iii) 1 %, a fourth group (iv) received saline injections, and another (v) no injections. The fellow eye was left untreated. An additional group received no treatment to either eye. Prior to and at the end of the treatment period, refraction and ocular biometry were performed. Results Visual deprivation produced relative myopia in all groups (treated versus untreated eyes, P < 0.05). The amount of myopia was significantly affected by the drug treatment (one-way ANOVA, P < 0.0001); myopia was less in deprived eyes receiving either 0.3 % or 1 % TPMPA (saline = −4.38 ± 0.57D, 0.3 % TPMPA = −3.00 ± 0.48D, P < 0.01; 1 % TPMPA = −0.88 ± 0.51D, P < 0.001). The degree of axial elongation was correspondingly less (saline = 0.13 ± 0.02 mm, 0.3 % TPMPA = 0.09 ± 0.01 mm, P < 0.01, 1 % TPMPA = 0.02 ± 0.01 mm, P < 0.001) as was the VC elongation (saline = 0.08 ± 0.01 mm, 0.3 % TPMPA = 0.05 ± 0.01 mm, P < 0.01, 1 % TPMPA = 0.01 ± 0.01 mm; P < 0.001). ACD and LT were not affected (one-way ANOVA, P > 0.05). One percent TPMPA was more effective at inhibiting myopia than 0.3 % (P < 0.01), and 0.03 % did not appreciably inhibit the myopia (0.03 % TPMPA versus saline, P > 0.05). Conclusions Sub-conjunctival injections of TPMPA inhibit FDM in guinea pig models in a dose-dependent manner.

Amplitude of accommodation in type 1 diabetes

Purpose People with diabetes have accelerated age-related biometric ocular changes compared with people without diabetes. We determined the effect of Type 1 diabetes on amplitude of accommodation. Method There were 43 participants (33 ± 8 years) with type 1 diabetes and 32 (34 ± 8 years) age-balanced participants without diabetes. There was no significant difference in the mean equivalent refractive error and visual acuity between the two groups. Amplitude of accommodation was measured using two techniques: objective — by determining the accommodative response to a stimulus in a COAS-HD wavefront aberrometer (Wavefront Sciences), and subjective — with a Badal hand optometer (Rodenstock). The influences of age and diabetes duration (in years) on amplitude of accommodation were analyzed using multiple regression analysis. Results Across both groups, objective amplitude was less than subjective amplitude by 1.4 ± 1.2 D. People with diabetes had lower objective (2.7 ± 1.6 D) and subjective (4.0 ± 1.7 D) amplitudes than people without diabetes (objective 4.1 ± 2.1 D, subjective 5.6 ± 2.1 D). For objective amplitude and the whole group, the duration of diabetes contributed 57% of the variation as did age. For the objective amplitude and only the diabetes group this was 78%. For subjective amplitude, the corresponding proportions were 68% and 103%. Conclusions Both objective and subjective techniques showed lowered amplitude of accommodation in participants with type 1 diabetes when compared with age-matched controls. The loss correlated strongly with duration of diabetes. The results suggest that individuals with diabetes will experience presbyopia earlier in life than people without diabetes, possibly due to metabolic changes in the lens.

Natural history of corneal nerve morphology in mild neuropathy associated with type 1 diabetes : Development of a potential measure of diabetic peripheral neuropathy

Purpose To investigate longitudinal changes of subbasal nerve plexus (SNP) morphology and its relationship with conventional measures of neuropathy in individuals with diabetes. Methods A cohort of 147 individuals with type 1 diabetes and 60 age-balanced controls underwent detailed assessment of clinical and metabolic factors, neurologic deficits, quantitative sensory testing, nerve conduction studies and corneal confocal microscopy at baseline and four subsequent annual visits. The SNP parameters included corneal nerve fiber density (CNFD), branch density (CNBD) and fiber length (CNFL) and were quantified using a fully-automated algorithm. Linear mixed models were fitted to examine the changes in corneal nerve parameters over time. Results At baseline, 27% of the participants had mild diabetic neuropathy. All SNP parameters were significantly lower in the neuropathy group compared to controls (P<0.05). Overall, 89% of participants examined at baseline also completed the final visit. There was no clinically significant change to health and metabolic parameters and neuropathy measures from baseline to the final visit. Linear mixed model revealed a significant linear decline of CNFD (annual change rate, -0.9 nerve/mm2, P=0.01) in the neuropathy group compared to controls, which was associated with age (β=-0.06, P=0.04) and duration of diabetes (β=-0.08, P=0.03). In the neuropathy group, absolute changes of CNBD and CNFL showed moderate correlations with peroneal conduction velocity and cold sensation threshold, respectively (rs, 0.38 and 0.40, P<0.05). Conclusion This study demonstrates dynamic small fiber damage at the SNP, thus providing justification for our ongoing efforts to establish corneal nerve morphology as an appropriate adjunct to conventional measures of DPN.

Corneal confocal microscopy shown an improvement in small-fibre neuropathy in subjects with type 1 diabetes on continuous subcutaneous insulin infusion compared to multiple daily injection

Improved glycemic control is the only treatment that has been shown to be effective for diabetic peripheral neuropathy in patients with type 1 diabetes (1). Continuous subcutaneous insulin infusion (CSII) is superior to multiple daily insulin injection (MDI) for reducing HbA1c and hypoglycemic events (2). Here, we have compared the benefits of CSII compared withMDI for neuropathy over 24months....

Altering the redox state of skeletal muscle by glutathione depletion increases the exercise-activation of PGC-1α

We investigated the relationship between mitochondrial biogenesis, cell signalling and antioxidant enzymes by depleting skeletal muscle glutathione with diethyl maleate (DEM) which resulted in a demonstrable increase in oxidative stress during exercise. Animals were divided into six groups: (1) sedentary control rats; (2) sedentary rats treated with DEM; (3) exercise control rats euthanized immediately after exercise; (4) exercise rats + DEM; (5) exercise control rats euthanized 4 h after exercise, and; (6) exercise rats + DEM euthanized 4 h after exercise. Exercising animals ran on the treadmill at a 10% gradient at 20 m/min for the first 30 min. The speed was then increased every 10 min by 1.6 m/min until exhaustion. There was a reduction in total glutathione in the skeletal muscle of DEM treated animals compared to the control animals (P<0.05). Within the control group, total glutathione was higher in the sedentary group compared to after exercise (P<0.05). DEM treatment also significantly increased oxidative stress, as measured by increased plasma F2-isoprostanes (P<0.05). Exercising animals given DEM showed a significantly greater increase in peroxisome proliferator activated receptor γ coactivator-1α(PGC-1α) mRNA compared to the control animals that were exercised (P<0.05). This study provides novel evidence that by reducing the endogenous antioxidant glutathione in skeletal muscle and inducing oxidative stress through exercise, PGC-1α gene expression was augmented. These findings further highlight the important role of exercise induced oxidative stress in the regulation of mitochondrial biogenesis.

Long-term outcomes following Medtronic Open Pivot valved conduit

Aortic root replacement is a complex procedure, though subsequent modifications of the original Bentall procedure have made surgery more reproducible. The study aim was to examine the outcomes of a modified Bentall procedure, using the Medtronic Open PivotTM valved conduit. Whilst short-term data on the conduit and long-term data on the valve itself are available, little is known of the long-term results with the valved conduit. Patients undergoing aortic root replacement between February 1999 and February 2010, using the Medtronic Open Pivot valved conduit were identified from the prospectively collected Cardiothoracic Register at The Prince Charles Hospital, Brisbane, Australia. All patients were followed up echocardiographically and clinically. The primary end-point was death, and a Cox proportional model was used to identify factors associated.with survival. Secondary end-points were valve-related morbidity (as defined by STS guidelines) and postoperative morbidity. Predictors of morbidity were identified using logistic regression. A total of 246 patients (mean age 50 years) was included in the study. The overall mortality was 12%, with actuarial 10-year survival 79% and a 10-year estimate of valve-related death of 0.04 (95% CI: 0.004, 0.07). Preoperative myocardial infarction (p = 0.004, HR 4.74), urgency of operation (p = 0.038, HR 2.8) and 10% incremental decreases in ejection fraction (p = 0.046, HR 0.69) were predictive of mortality. Survival was also affected by the valve gradients, with a unit increase in peak gradient reducing mortality (p = 0.021, HR 0.93). Valve-related morbidity occurred in 11 patients. Urgent surgery (p <0.001, OR 4.12), aortic dissection (p = 0.015, OR 3.35), calcific aortic stenosis (p = 0.016, OR 2.35) and Marfan syndrome (p 0.009, OR 3.75) were predictive of postoperative morbidity. The reoperation rate was 1.2%. The Medtronic Open Pivot valved conduit is a safe and durable option for aortic root replacement, and is associated with low morbidity and 10-year survival of 79%. However, further studies are required to determine the effect of valve gradient on survival.

The prolongation of length of stay because of Clostridium difficile infection

Background Clostridium difficile infection (CDI) possibly extends hospital length of stay (LOS); however, the current evidence does not account for the time-dependent bias, ie, when infection is incorrectly analyzed as a baseline covariate. The aim of this study was to determine whether CDI increases LOS after managing this bias. Methods We examined the estimated extra LOS because of CDI using a multistate model. Data from all persons hospitalized >48 hours over 4 years in a tertiary hospital in Australia were analyzed. Persons with health care-associated CDIs were identified. Cox proportional hazards models were applied together with multistate modeling. Results One hundred fifty-eight of 58,942 admissions examined had CDI. The mean extra LOS because of infection was 0.9 days (95% confidence interval: −1.8 to 3.6 days, P = .51) when a multistate model was applied. The hazard of discharge was lower in persons who had CDI (adjusted hazard ratio, 0.42; P < .001) when a Cox proportional hazard model was applied. Conclusion This study is the first to use multistate models to determine the extra LOS because of CDI. Results suggest CDI does not significantly contribute to hospital LOS, contradicting findings published elsewhere. Conversely, when methods prone to result in time-dependent bias were applied to the data, the hazard of discharge significantly increased. These findings contribute to discussion on methods used to evaluate LOS and health care-associated infections.

Public space for street-scape theatrics : guerrilla spatial tactics and methods of urban hacking in Brisbane, Australia

It could be argued that architecture has an inherent social responsibility to enrich the urban and spatial environments for the city’s occupants. However how we define quality, and how ‘places’ can be designed to be fair and equitable, catering for individuals on a humanistic and psychological level, is often not clearly addressed. Lefebvre discusses the idea of the ‘right to the city’; the belief that public space design should facilitate freedom of expression and incite a sense of spatial ownership for its occupants in public/commercial precincts. Lefebvre also points out the importance of sensory experience in the urban environment. “Street-scape theatrics” are performative activities that summarise these two concepts, advocating the ‘right to the city’ by way of art as well as providing sensual engagement for city users. Literature discusses the importance of Street-scape Theatrics however few sources attempt to discuss this topic in terms of how to design these spaces/places to enhance the city on both a sensory and political level. This research, grounded in political theory, investigates the case of street music, in particular busking, in the city of Brisbane, Australia. Street culture is a notion that already exists in Brisbane, but it is heavily controlled especially in central locations. The study discusses how sensory experience of the urban environment in Brisbane can be enriched through the design for busking; multiple case studies, interviews, observations and thematic mappings provide data to gather an understanding of how street performers see and understand the built form. Results are sometime surprisingly incongruous with general assumptions in regards to street artist as well as the established political and ideological framework, supporting the idea that the best and most effective way of urban hacking is working within the system. Ultimately, it was found that the Central Business District in Brisbane, Australia, could adopt certain political and design tactics which attempt to reconcile systematic quality control with freedom of expression into the public/commercial sphere, realism upheld. This can bridge the gap between the micro scale of the body and the macro of the political economy through freedom of expression, thus celebrating the idiosyncratic nature of the city.

Urban Form at the Edge : Proceedings from ISUF 2013 [Volume 1]

Urban morphology as a field of study has developed primarily in Europe and North America, and more recently emerging as a recurrent topic in China and South America. As a counterpoint to this centric view, the ISUF 2013 conference explored aspects of ‘urban form at the edge’. In particular the conference examined ‘off centre areas’ such as India, Africa, Middle East, Central Asia and Australasia which require innovative approaches to the study of traditional, as well as post-colonial and contemporary, morphologies. Broader interpretations of urban form at the edge focus on minor centres and suburbia, with their developing and transilient character; edge cities and regional centres; and new technologies and approaches that are developing alongside established methods, tools and theories of urban morphology...

Structuring representations of continuous data through investigations in grade 1

The study of data modelling with elementary students involves the analysis of a developmental process beginning with children’s investigations of meaningful contexts: visualising, structuring, and representing data and displaying data in simple graphs (English, 2012; Lehrer & Schauble, 2005; Makar, Bakker, & Ben-Zvi, 2011). A 3-year longitudinal study investigated young children’s data modelling, integrating mathematical and scientific investigations. One aspect of this study involved a researcher-led teaching experiment with 21 mathematically able Grade 1 students. The study aimed to describe explicit developmental features of students’ representations of continuous data...

Confirmatory factor analysis and invariance testing of the Young Carer of Parents Inventory (YCOPI)

Objective Research into youth caregiving in families where a parent experiences a significant medical condition has been hampered by a lack of contextually sensitive measures of the nature and breadth of young caregiving experiences. This study examined the factor structure and measurement invariance of such a measure called the Young Carer of Parents Inventory (YCOPI; Pakenham et al., 2006) using confirmatory factor analysis across 3 groups of youth. The YCOPI has 2 parts: YCOPI-A with 5 factors assessing caregiving experiences that are applicable to all caregiving contexts; YCOPI-B with 4 factors that tap dimensions related to youth caregiving in the context of parent illness. Design Two samples (ages 9–20 years) were recruited: a community sample of 2,429 youth from which 2 groups were derived (“healthy” family [HF], n = 1760; parental illness [PI], n = 446), and a sample of 130 youth of a parent with multiple sclerosis). Results With some modification, the YCOPI-A demonstrated a replicable factor structure across 3 groups, and exhibited only partial measurement invariance across the HF and PI groups. The impact of assuming full measurement invariance on latent mean differences appeared small, supporting use of the measure in research and applied settings when estimated using latent factors and controlling for measurement invariance. PI youth reported significantly higher scores than did HF youth on all YCOPI-A subscales. The YCOPI-B requires some modifications, and further development work is recommended. Conclusion The factor structure that emerged and the addition of new items constitutes the YCOPI-Revised. Findings support the use of the YCOPI-Revised in research and applied settings.

The spectrum of HIV-1 related cancers in South Africa

Despite the high prevalence of infection by the Human Immunodeficiency Virus (HIV) in South Africa, information on its association with cancer is sparse. Our study was carried out to examine the relationship between HIV and a number of cancer types or sites that are common in South Africa. A total of 4,883 subjects, presenting with a cancer or cardiovascular disease at the 3 tertiary referral hospitals in Johannesburg, were interviewed and had blood tested for HIV. Odds ratios associated with HIV infection were calculated by using unconditional logistic regression models for 16 major cancer types where data was available for 50 or more patients. In the comparison group, the prevalence of HIV infection was 8.3% in males and 9.1% in females. Significant excess risks associated with HIV infection were found for Kaposi's sarcoma (OR=21.9, 95% CI=12.5–38.6), non-Hodgkin lymphoma (OR=5.0, 95%CI=2.7–9.5), vulval cancer (OR=4.8, 95%CI=1.9–12.2) and cervical cancer (OR=1.6, 95%CI=1.1–2.3) but not for any of the other major cancer types examined, including Hodgkin disease, multiple myeloma and lung cancer. In Johannesburg, South Africa, HIV infection was associated with significantly increased risks of Kaposi's sarcoma, non-Hodgkin lymphoma and cancers of the cervix and the vulva. The relative risks for Kaposi's sarcoma and non-Hodgkin lymphoma associated with HIV infection were substantially lower than those found in the West.