43 resultados para redox cycling
Resumo:
Issue addressed: Although increases in cycling in Brisbane are encouraging, bicycle mode share to work in the state of Queensland remains low. The aim of this qualitative study was to draw upon the lived experiences of Queensland cyclists to understand the main motivators for utility cycling (cycling as a means to get to and from places) and compare motivators between utility cyclists (those who cycle for utility as well as for recreation) and non-utility cyclists (those who cycle only for recreation). Methods: For an online survey, members of a bicycle group (831 utility cyclists and 931 non-utility cyclists, aged 18-90 years) were asked to describe, unprompted, what would motivate them to engage in utility cycling (more often). Responses were coded into themes within four levels of an ecological model. Results: Within an ecological model, built environment influences on motivation were grouped according to whether they related to appeal (safety), convenience (accessibility) or attractiveness (more amenities) and included adequate infrastructure for short trips, bikeway connectivity, end-of-trip facilities at public locations and easy and safe bicycle access to destinations outside of cities. A key social-cultural influence related to improved interactions among different road users. Conclusions: The built and social-cultural environments need to be more supportive of utility cycling before even current utility and non-utility cyclists will be motivated to engage (more often) in utility cycling. So what?: Additional government strategies and more and better infrastructure that support utility cycling beyond commuter cycling may encourage a utility cycling culture.
Resumo:
OBJECTIVE Interest is growing in promoting utility cycling (i.e., for transport) as a means of incorporating daily physical activity (PA) into people’s lives, but little is known about correlates of utility cycling. Our primary aim was to examine cross-sectional relationships between socio-economic characteristics, neighborhood environment perceptions and psychological disposition with utility cycling (with or without additional recreational cycling). A secondary aim was to compare these relationships with those for recreation-only cycling. METHOD Baseline survey data (2007) from 10,233 participants in HABITAT, a multilevel longitudinal study of PA, sedentary behavior, and health in Brisbane adults aged 40-65 years, were analysed using multinomial regression modelling. RESULTS Greater income, habitual PA, and positive beliefs about PA were associated with utility and recreation-only cycling (p<0.05). Always having vehicle access and not in the labor force were associated with recreation-only cycling (p<0.05). Some or no vehicle access, part-time employment, and perceived environmental factors (little crime, few cul-de-sacs, nearby transport and recreational destinations) were associated with utility cycling (p<0.05). CONCLUSION Our findings suggest differences in associations between socio-economic, neighborhood perceptions and psychological factors and utility and recreation-only cycling in Brisbane residents aged 40-65 years. Tailored approaches appear to be required to promote utility and recreational cycling.
Resumo:
Abstract Ag-TiO2 and Au-TiO2 hybrid electrodes were designed by covalent attachment of TiO2 nanoparticles to Ag or Au electrodes via an organic linker. The optical and electronic properties of these systems were investigated using the cytochrome b5 (Cyt b5) domain of sulfite oxidase, exclusively attached to the TiO2 surface, as a Raman marker and model redox enzyme. Very strong SERR signals of Cyt b 5 were obtained for Ag-supported systems due to plasmonic field enhancement of Ag. Time-resolved surface-enhanced resonance Raman spectroscopic measurements yielded a remarkably fast electron transfer kinetic (k = 60 s -1) of Cyt b5 to Ag. A much lower Raman intensity was observed for Au-supported systems with undefined and slow redox behavior. We explain this phenomenon on the basis of the different potential of zero charge of the two metals that largely influence the electronic properties of the TiO2 island film. © 2013 American Chemical Society.
Resumo:
Roundabouts reduce the frequency and severity of motor vehicle crashes and therefore the number installed has increased dramatically in the last 20 years in many countries. However, the safety impacts of roundabouts for bicycle riders are a source of concern, with many studies reporting lower injury reductions for cyclists than car occupants. This paper summarises the results of a project undertaken to provide guidance on how cyclist safety could be improved at existing roundabouts in Queensland, Australia, where cyclist crashes have been increasing and legislation gives motor vehicles priority over cyclists and pedestrians at roundabouts. The review of international roundabout design guidelines identified two schools of design: tangential roundabouts (common in English-speaking countries, including Australia), which focus on minimising delay to motor vehicles, and radial roundabouts (common in continental Europe), which focus on speed reduction and safety. While it might be expected that radial roundabouts would be safer for cyclists, there have been no studies to confirm this view. Most guidelines expect cyclists to act as vehicle traffic in single-lane, typically low-speed, roundabouts. Some jurisdictions do not permit cyclists to travel on multi-lane roundabouts, and recommend segregated bicycle facilities because of their lowest crash risk for cyclists. Given that most bicycle-vehicle crashes at roundabouts involve an entering vehicle and a circulating cyclist, the greatest challenges appear to be reducing the speed of motor vehicles on the approach/entry to roundabouts and other ways of maximizing the likelihood that cyclists will be seen. Lower entry speeds are likely to underpin the greater safety of compact roundabouts for cyclists and, conversely, the higher than expected crash rates at two-lane roundabouts. European research discourages the use of bike lanes in roundabouts which position cyclists at the edge of the road and contributes to cyclists being less likely to be noticed by drivers.
Resumo:
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.
Resumo:
There is growing interest in the biomechanics of ‘fusionless’ implant constructs used for deformity correction in the thoracic spine, however, there are questions over the comparability of in vitro biomechanical studies from different research groups due to the various methods used for specimen preparation, testing and data collection. The aim of this study was to identify the effect of two key factors on the stiffness of immature bovine thoracic spine motion segments: (i) repeated cyclic loading and (ii) multiple freeze-thaw cycles, to aid in the planning and interpretation of in vitro studies. Two groups of thoracic spine motion segments from 6-8 week old calves were tested in flexion/extension, right/left lateral bending, and right/left axial rotation under moment control. Group (A) were tested with continuous repeated cyclic loading for 500 cycles with data recorded at cycles 3, 5, 10, 25, 50, 100, 200, 300, 400 and 500. Group (B) were tested after each of five freeze-thaw sequences, with data collected from the 10th load cycle in each sequence. Group A: Flexion/extension stiffness reduced significantly over the 500 load cycles (-22%; P=0.001), but there was no significant change between the 5th and 200th load cycles. Lateral bending stiffness decreased significantly (-18%; P=0.009) over the 500 load cycles, but there was no significant change in axial rotation stiffness (P=0.137). Group B: There was no significant difference between mean stiffness over the five freeze-thaw sequences in flexion/extension (P=0.813) and a near significant reduction in mean stiffness in axial rotation (-6%; P=0.07). However, there was a statistically significant increase in stiffness in lateral bending (+30%; P=0.007). Comparison of in vitro testing results for immature thoracic bovine spine segments between studies can be performed with up to 200 load cycles without significant changes in stiffness. However, when testing protocols require greater than 200 cycles, or when repeated freeze-thaw cycles are involved, it is important to account for the effect of cumulative load and freeze-thaw cycles on spine segment stiffness.
Resumo:
Over recent years, the health, transport and environment sectors have been increasingly focused on the promotion of transport cycling. From a health perspective, transport cycling is recognised as a beneficial form of physical activity as it can be easily integrated into daily living, is done at an intensity that confers health benefits, and is associated with reductions in mortality and morbidity [1]. From a safety perspective, the risk of a serious cycling injury decreases as cycling increases [2] as having more cyclists on roads increases motor vehicle drivers’ awareness of cyclists and in turn makes cycling safer. Whereas cycling for recreation is the fourth most commonly reported physical activity among Australian adults [3], transport cycling is an underutilised travel mode. Approximately 1.3% of journeys to work in Australia are made by bicycle [4]. This low prevalence is mirrored in the UK and the US, but not in some European countries like the Netherlands and Denmark, where over 18% and 26%, respectively, of all journeys are made by bicycle [5]. In the past decade, concerted efforts have been made by Australian state and local governments to increase cycling rates [6]. Notably, Melbourne, Sydney and Brisbane have implemented policies, increased bicycle commuting infrastructure, and offered information and promotion programs to encourage commuter cycling [6,7]. Governments have also developed comprehensive longterm plans for guiding future cycling strategies, using lessons learned from around the world in developing successful cycling policy and promotion [6,7]. Changes in transport cycling rates in inner cities since these efforts have been implemented are encouraging. In Sydney, census data indicate an 83% increase in the number of people using a bicycle for commuting between 2001 and 2011 [8]. Counts of bicycles being ridden along major cycling commuter routes indicate increases in weekday morning cycling trips in Brisbane (63% increase from 2004 to 2010) [7] and in Melbourne (a 43% increase from 2006 to 2008) [9]. However, bicycle mode share to work has changed little: for example, between 2001 and 2011, it decreased slightly from 1.6% to 1.3% in Brisbane [10,11]. Researchers have been investigating factors that may be contributing to low rates of cycling for transport, to inform future policy and programming to encourage transport cycling. The aim of this paper is to overview our work to date in this area of research in Queensland.
Resumo:
The synthesis, electronic absorption and 1H NMR spectra of a suite of novel porphyrinoids derived from meso-bromoporphyrins by palladium-catalysed aminations using ethyl and tert-butylcarbazates are reported. Instead of the expected carbazate-substituted porphyrins, a facile oxidative dearomatisation of the porphyrin ring occurs in high yield, especially for the nickel(II) complexes, resulting in high yields of 5,15-diiminoporphodimethenes (DIPDs). The analogous zinc(II) and free base DIPDs were also characterised, the former by X-ray crystallography. The oxidation and reduction reactions of DIPDs and their precursor carbazate porphyrins were studied. Density Functional Theory (DFT) was used to calculate the optimised geometries and frontier molecular orbitals of DIPD Ni8c and bis(azocarboxylate) 19c, and Time Dependent DFT calculations allowed the prediction of electronic absorption spectra, whose characteristics corresponded well with those of the observed solution spectra. In the latter case, the calculated low-energy absorptions were unlike those of a typical porphyrin, due to the near-degeneracy of the highest filled frontier orbitals, and the wide energy separation between the unfilled orbitals. This feature was present in the observed spectrum.
Resumo:
The current study introduces a novel synthetic avenue for the preparation of profluorescent nitroxides via nitrile imine-mediated tetrazole-ene cycloaddition (NITEC). The photoinduced cycloaddition was performed under metal-free, mild conditions allowing the preparation of a library of the nitroxide functionalized pyrazolines and corresponding methoxyamines. High reaction rates and full conversion were observed, with the presence of the nitroxide having no significant impact on the cycloaddition performance. The formed products were investigated with respect to their photophysical properties in order to quantify their “switch on/off” behavior. The fluorescence quenching performance is strongly dependent on the distance between the chromophore and the free radical spin as demonstrated theoretically and experimentally. Highest levels of fluorescence quenching were achieved for pyrazolines with the nitroxide directly fused to the chromophore. Importantly, the pyrazoline profluorescent nitroxides were shown to efficiently act as sensors for redox/radical processes.
Resumo:
Cyclists are among the most vulnerable road users. Many recent interventions have aimed at improving their safety on the road, such as the minimum overtaking distance rule introduced in Queensland in 2014. Smartphones offer excellent opportunities for technical intervention for road safety at a limited cost. Indeed, they have a lot of available processing power and many embedded sensors that allow analysing a rider's (or driver's) motion, behaviour, and environment; this is especially relevant for cyclists, as they do not have the space or power allowance that can be found in most motor vehicles. The aim of the study presented in this paper is to assess cyclists’ support for a range of new smartphone-based safety technologies. The preliminary results for an online survey with cyclists recruited from Bicycle Queensland and Triathlon Queensland, with N=191, are presented. A number of innovative safety systems such as automatic logging of incidents without injuries, reporting of dangerous area via a website/app, automatic notification of emergency services in case of crash or fall, and advanced navigation apps were assessed. A significant part of the survey is dedicated to GoSafeCycle, a cooperative collision prevention app based on motion tracking and Wi-Fi communications developed at CARRS-Q. Results show a marked preference toward automatic detection and notification of emergencies (62-70% positive assessment) and GoSafeCycle (61.7% positive assessment), as well as reporting apps (59.1% positive assessment). Such findings are important in the context of current promotion of active transports and highlight the need for further development of system supported by the general public.
Resumo:
This study examined associations between objective environmental attributes and, separately, transport (TC) and recreational cycling (RC). Environmental attributes were more strongly associated with TC than RC. Distances to areas with the best bicycle infrastructure and urban amenities may be key environmental factors influencing TC but not RC. Government investments in bicycle infrastructure within inner Brisbane appear to have resulted in more TC than in outer areas and to appeal to residents of both the most and least disadvantaged neighbourhoods. Extending this infrastructure to residents living in disadvantaged and advantaged neighbourhoods outside the CBD could expand TC participation.
Resumo:
Review conducted as part of a Queensland Department of Transport and Main Roads funded project ‘Roundabout design review’. The project examined: - Design guidelines - Factors that affect safety at roundabouts