Ionic liquid effects on the redox potential of ferrocene

The ionic liquid, IL, dependence of the mid-point potential of the ferrocene|ferrocenium, Fc^0/+, couple versus the decamethylferrocene|decamethylferrocenium, DmFc^0/+, couple was studied in eleven ILs and in dichloromethane with added IL as the supporting electrolyte. The difference in mid-point potential between Fc and DmFc indicates that Fc^0/+ couple is clearly dependent on the IL structure. A variation of about 0.100 V over the range of ILs studied under neat conditions and by ca. 0.050 V when studied in dichloromethane is reported. Meanwhile, a variable potential shift ranging from 0.014 to 0.082 V was observed when data was compared in these two systems (ILs vs. dichloromethane). The effect of water and lithium ion on the Fc^0/+ and DmFc^0/+ redox potential was also evaluated and found to be minimal.

Characterization of decamethylferrocene and ferrocene in ionic liquids : Argon and vacuum effect on their electrochemical propertiesce

The electrochemistry of decamethylferrocene (DmFc) has been studied in organic solvent systems and proven to be a superior internal reference redox standard to ferrocene (Fc). However, the electrochemical information on this redox couple in ionic liquids is still limited. Therefore, the voltammetric and amperometric behaviour of DmFc was investigated under argon and vacuum conditions in six different ionic liquids and compared to that of Fc under the same experimental conditions. Consequently, the concentration, the heterogeneous electron-transfer rate constant (k0), volatility, and diffusion coefficients (D) of Fc and Fc+, as well as the solubility, k 0, and D values for DmFc and DmFc+ were determined under argon and vacuum conditions by fitting the experimental chronoamperometric and voltammetric data with numerical and digital simulations. The rate of mass transport of ferrocene and decamethylferrocene was observed to decreases between 6-37% by changing the working atmosphere from argon to vacuum. The D Fc/DFc+ ratios are in the range 1.31-2.01 in the different ILs. Importantly, the DDmFc/DDmFc+ ratio is ≈ 1 in 1-methyl-3-butylimidazolium bis(trifluoromethylsulfonyl)amide, 1-methyl-1-butylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, and 1-methyl-3-ethylimidazolium tris(pentafluoroethyl)trifluorophosphate. The experimental mid-point potential and half-wave potential of Fc0/+ vs. DmFc0/+, as well as the formal potential obtained after correction for inequality in the respective diffusion coefficients of both redox processes are presented. Even though DmFc is not freely soluble in the different ILs, the results presented in this work suggest that the DmFc0/+ redox process is less dependent than Fc on the IL nature. This is a very relevant finding for the application of this transition-metal sandwich complex as an internal reference redox system in IL solutions. © 2014 Elsevier Ltd.

Balancing environmental impacts and benefits of wastewater reuse

Wastewater reuse is being widely promulgated to help address the global freshwater resource crisis. It can assist in reducing extraction of freshwater from the environment, and reuse of wastewater lessens the need for environmental discharge, which is clearly beneficial to receiving waters. But the practice itself also has the potential to be detrimental to natural and human environments: soil structure can become degraded, aquifers may be polluted, and human health may be threatened. The challenge facing natural resource managers is to identify the potential benefits and risks, and to achieve an appropriate balance. This paper describes environmental benefits and threats concomitant with the reuse of wastewater. We frequently draw upon examples from China and Australia-two countries that face particularly daunting water resource
challenges-but the principles can be.extended far beyond these geographical bounds and are applicable to
many parts of the world.

A preliminary examination of public opinion in Australia on the use of biometric devices or identifiers in everyday life

Since the September 11,2001 terrorist attacks in New York City, many countries including Australia have been able to justify the use of biometric devices for identification and surveillance of their own citizens and others in the name of national security.

This paper reports on the preliminary findings of a survey that examined Australians' views and experiences with the use of biometric devices in everyday situations in the context of their potential to serve as a 'Panopticon' to keep the nation's citizenry under surveillance. It discusses the adoption of the new communication technology from the point of view of the Justification model that sees technology choice as social
gambling and the pluralist view of technology that sees technology as neutral in itself but as having negative or positive effects on society based on how It is used.

The paper proposes the need for Australian society to balance citizens' right to privacy and civil liberties with the right to stay alive and safe from terrorism and how it may be done with the necessary legal and regulator)' safeguards.

Fluorescent photoinduced electron transfer (PET) sensors for anions; from design to potential application

This mini review highlights the synthesis and photophysical evaluation of anion sensors, for nonaqueous solutions, that have been developed in our laboratories over the last few years. We have focused our research mainly on developing fluorescent photoinduced electron transfer (PET) sensors based on the fluorophore-spacer-anion receptor principle using several anthracene (emitting in the blue) and 1,8-naphthalimide (emitting in the green) fluorophores, with the aim of targeting biologically and industrially relevant anions such as acetates, phosphate and amino acids, as well as halides such as fluoride. The receptors and the fluorophore are separated by a short methyl or ethyl spacer, where the charge neutral anion receptors are either aliphatic or aromatic urea (or thiourea) moieties. For these, the anion recognition is through hydrogen bonding, yielding anion:receptor complexes. Such bonding gives rise to enhanced reduction potential in the receptor moieties which causes enhancement in the rate of PET quenching of the fluorophore excited state from the anion:receptor moiety. This design can be further elaborated on by incorporating either two fluorophores, or urea/thiourea receptors into the sensor structures, using anthracene as a fluorophore. For the latter design, the sensors were designed to achieve sensing of bis-anions, such as di-carboxylates or pyrophosphate, where the anion bridged the anthracene moiety. In the case of the naphthalimide based mono-receptor based PET sensors, it was discovered that in DMSO the sensors were also susceptible to deprotonation by anions such as F− at high concentrations. This led to substantial changes in the absorption spectra of these sensors, where the solution changed colour from yellow/green to deep blue, which was clearly visible to the naked eye. Hence, some of the examples presented can act as dual fluorescent-colorimetric sensors for anions. Further investigations into this phenomenon led to the development of simple colorimetric sensors for fluorides, which upon exposure to air, were shown to fix carbon dioxide as bicarbonate.

Balancing comfort expectations and greenhouse gas emissions, thermal comfort in office buildings in a changing climate

According to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change (IPCC), the construction sector has the greatest potential for climate change mitigation. This work investigates the potential for climate change mitigation in naturally ventilated and mixed mode office buildings, by evaluating the range of influence of building design and occupants on greenhouse gas emissions as well as thermal and visual comfort.

Thermal comfort is evaluated according to the EN 15251 adaptive thermal comfort model, visual comfort is based on daylight autonomy and view. Parametric studies have been conducted based on building simulation for the climate of Athens, Greece. Input data are based on a literature review, and on results from a field study conducted among office occupants and architects in Athens.

The results show that the influence of occupants on greenhouse gas emissions is larger than the influence of building design. Energy saving office equipment, as well as active use of building controls for shading and lighting by occupants are crucial parameters regarding the reduction of CO2 emissions. In mixed mode buildings, the coefficient of performance of the cooling system is an important parameter as well. Regarding thermal and visual comfort, the influence of building design is predominant. A green building, well protected against heat from the sun and able to balance solar and internal heat gains, provides higher comfort levels and is less affected by the influence of occupants. In mixed mode buildings, building design is the predominant influence on the magnitude of cooling loads. A hot summer including heat waves can significantly reduce thermal comfort and increase the resulting greenhouse gas emissions. Green buildings are least affected by these influences.

The EN 15251 adaptive thermal comfort model provides a thermal comfort evaluation method valid throughout Europe. However, for the Mediterranean climate of Athens, Greece, most of the configurations investigated within this study do not meet the requirements according to this model. EN 15251 refers to an adaptive thermal comfort model for naturally ventilated and to a static model for mechanically ventilated buildings. For mixed mode buildings, the static model is recommended, but literature indicates that occupants in those buildings might be more tolerant towards higher temperatures. The hypothetical application of the EN 15251 adaptive thermal comfort model in mixed mode offices, as investigated in this study, shows potential for greenhouse gas emission savings. However, this influence is small compared to that of building design and occupants. Conclusions are drawn regarding the categorisation and exceeding criteria according to EN 15251 adaptive thermal comfort model for offices in a Mediterranean climate.

The results of this work show, that not only green buildings, but also green occupants can significantly contribute to the mitigation of the climate change. Mechanisms of the real estate market as well as the lifestyle of occupants are important influences in this context. Sustainability therefore refers to finding the right balance between occupant’s comfort expectations and resulting greenhouse gas emissions for a specific building, rather than optimisation of single parameters

Balancing buildings and occupants - a holistic approach to thermal comfort and greenhouse gas emissions in mixed mode offices

This paper describes a holistic approach to comfort and greenhouse gas emissions in mixed mode offices. It is based on parametric studies for a typical cellular office in the Mediterranean climate of Athens, Greece, using building simulation.

Considered parameters are the influence of different building design, varying occupant behaviour and internal heat loads, as well as of an exceptionally hot summer. Additionally, the performance of a cooling strategy following the comfort limits according to the EN 15251 adaptive model is compared with the common fixed cooling set point 22°C.

The performance of mixed mode offices is evaluated regarding thermal comfort, daylight autonomy and related greenhouse gas emissions. Results indicate strategies to improve sustainability in mixed mode offices in Athens, by balancing the influencing parameters.

Sustainable retrofit potential in lower quality office stock in the central business district

Given the relationship between energy consumption, greenhouse gas emissions and climate change, the built environment has significant potential to lessen overall emissions. With around half of all greenhouse gas emissions attributed to the built environment; it has a significant role to play in mitigating global warming. With large percentages of office stock structurally vacant in some city centres and only 1 or 2% of new buildings added to the total stock each year; the scope for reductions lay with adaptation of existing buildings. The stock with the highest levels of vacancy and obsolescence offers the highest potential of all.

Many cities are now aiming to become carbon neutral. Successful retrofit demands that social, technological, environmental, economic and legislative criteria are addressed. Buildings have to meet user and community needs. City centres comprise a range of different type of office stock with regards to age, size, location, height, tenure and quality. All buildings present challenges and opportunities with regards to retrofit and sustainability and integrating retrofit measures that reduce energy, water and resource consumption.

Using a selection of low grade office buildings to develop retrofit profiles, this paper addresses the questions; (a) what is the nature of retrofits in relation to low quality office building stock in the Central Business District (CBD) and, (b) what is the extent and scope for sustainable retrofits to low quality office buildings. Using Melbourne CBD retrofit events of low quality office buildings were analysed between 1998 and 2008 to identify the scope and extent for integrating sustainability into retrofits projects.

Balancing the benefits and risks of public–private partnerships to address the global double burden of malnutrition

Objective: Transnational food, beverage and restaurant companies, and their corporate foundations, may be potential collaborators to help address complex public health nutrition challenges. While UN system guidelines are available for private-sector engagement, non-governmental organizations (NGO) have limited guidelines to navigate diverse opportunities and challenges presented by partnering with these companies through public–private partnerships (PPP) to address the global double burden of malnutrition.

Design: We conducted a search of electronic databases, UN system websites and grey literature to identify resources about partnerships used to address the global double burden of malnutrition. A narrative summary provides a synthesis of the interdisciplinary literature identified.

Results: We describe partnership opportunities, benefits and challenges; and tools and approaches to help NGO engage with the private sector to address global public health nutrition challenges. PPP benefits include: raising the visibility of nutrition and health on policy agendas; mobilizing funds and advocating for research; strengthening food-system processes and delivery systems; facilitating technology transfer; and expanding access to medications, vaccines, healthy food and beverage products, and nutrition assistance during humanitarian crises. PPP challenges include: balancing private commercial interests with public health interests; managing conflicts of interest; ensuring that co-branded activities support healthy products and healthy eating environments; complying with ethical codes of conduct; assessing partnership compatibility; and evaluating partnership outcomes.

Conclusions: NGO should adopt a systematic and transparent approach using available tools and processes to maximize benefits and minimize risks of partnering with transnational food, beverage and restaurant companies to effectively target the global double burden of malnutrition.

The potential to reduce the embodied energy in construction through the use of renewable materials

The threat of dangerous levels of global warming demand that we significantly reduce carbon emissions over the coming decades. Globally, carbon emissions from all energy end-uses in buildings in 2004 were estimated to be 8.6 Gt CO2 or almost one quarter of total CO2 emissions (IPCC 2007). In Australia, nearly ten per cent of greenhouse gases come from the residential sector (DCCEE 2012). However, it is not merely the operation of the buildings that contributes to their CO2 emissions, but the energy used over their entire life cycle. Research has demonstrated that the embodied energy of the construction materials used in a building can sometimes equal the operational energy over the building’s entire lifetime (Crawford 2011). Therefore the materials used in construction need to be carefully considered. Conventional building materials not only represent high levels of embodied energy but also use resources that are finite and are being depleted. Renewable building materials are those materials that can be regenerated quickly enough to remove the threat of depletion and in theory their production could be carbon-neutral. To assess the potential for renewable building materials to reduce the embodied energy content of residential construction, the embodied energy of a small residential building has been determined. Wherever possible, the conventional construction materials were then replaced by commercially-available renewable building materials. The embodied energy of the building was then recalculated. The analysis showed that the embodied energy of the building could be reduced from 7.5 GJ per m2 to 5.4 GJ per m2 i.e. by 28%. The commercial availability of renewable materials, however, was a limiting factor and indicated that the industry is not yet well positioned to embrace this strategy to reduce embodied energy of construction. While some conventional building materials could readily be replaced, in many instances a renewable substitute could not be found.

Consumer acceptability and antioxidant potential of probiotic-yogurt with spices

The study focuses on developing novel probiotic yogurts containing spices with acceptable sensory properties, therapeutic levels of probiotics and with beneficial antioxidant capacity. Eight types of yogurts with added spice oleoresins (cardamom, cinnamon and nutmeg) and probiotics [Lactobacillus acidophilus strain 5(LA5), or Bifidobacterium animalisssp.Lactis (Bb12)] were produced. Two successive consumer sensory taste panels (n = 54) using a nine point hedonic scale were conducted to evaluate the acceptability of the yogurts. Viable counts of probiotics and antioxidant capacity of yogurt samples at 1, 7, 14 and 28 days of storage at 4 °C were monitored. The probiotic-yogurt products containing spices showed good sensory properties, with the best results obtained with cardamom oleoresin (with LA5 or Bb12). The presence of spice oleoresins (cardamom, nutmeg and cinnamon) did not affect the probiotic population (LA5or Bb12) in yogurt during 4 weeks of refrigerated storage. The antioxidant capacity (with LA5or Bb12) over the storage period was also maintained.

Drivers display anger-congruent attention to potential traffic hazards

Previous research has suggested that angry drivers may respond differently to potential hazards. This study replicates and extends these findings. Under simulated driving conditions, two groups of drivers experienced conditions that would either increase angry mood (N=12; men =6) or not (control group, N =12; men=6). All drivers then performed a neutral drive, during which they encountered a number of traffic events not experienced in the initial drive. These included vehicles emerging from driveways into their path and jaywalking pedestrians. Subjective anger, eye-movement behaviour and driving behaviours (speed and reaction times) were measured as drivers drove. Subjective moods (Profile of Mood States) were assessed before and after each drive. Anger-provoked drivers reported reliably higher increases in angry mood when compared with the control group after the initial drive, and these increases remained stable across the subsequent neutral drive. During the neutral drive, anger provoked drivers demonstrated evidence of more heuristic style processing of potential hazards, with shorter initial gazes at less apparent hazards and longer latencies to look back at jaywalking pedestrians obscured by parked vehicles. Anger-provoked drivers also took longer to make corrective actions to avoid potential collisions. It is concluded that anger-provoked drivers may initially make more superficial assessments of certain driving situations and consequently underestimate the inherent risk.

The 0-1 Knapsack polytope – a starting point for cryptanalysis of Knapsack ciphers?

The Knapsack Cryptosystem of Merkle and Hellman, 1978, is one of the earliest public-key cryptography schemes. The security of the method relies on the difficulty in solving Subset Sum Problems (also known as Knapsack Problems). In this paper, we first provide a brief history of knapsack-based cryptosystems and their cryptanalysis attacks. Following that, we review the advances in integer programming approaches to 0 − 1 Knapsack Problems, with a focus on the polyhedral studies of the convex hull of the integer set. Last of all, we discuss potential future research directions in applying integer programming in the cryptanalysis of knapsack ciphers.

Severe hypoglycaemia in type 1 diabetes mellitus: underlying drivers and potential strategies for successful prevention

Hypoglycaemia remains an over-riding factor limiting optimal glycaemic control in type 1 diabetes. Severe hypoglycaemia is prevalent in almost half of those with long-duration diabetes and is one of the most feared diabetes-related complications. In this review, we present an overview of the increasing body of literature seeking to elucidate the underlying pathophysiology of severe hypoglycaemia and the limited evidence behind the strategies employed to prevent episodes. Drivers of severe hypoglycaemia including impaired counter-regulation, hypoglycaemia-associated autonomic failure, psychosocial and behavioural factors and neuroimaging correlates are discussed. Treatment strategies encompassing structured education, insulin analogue regimens, continuous subcutaneous insulin infusion pumps, continuous glucose sensing and beta-cell replacement therapies have been employed, yet there is little randomized controlled trial evidence demonstrating effectiveness of new technologies in reducing severe hypoglycaemia. Optimally designed interventional trials evaluating these existing technologies and using modern methods of teaching patients flexible insulin use within structured education programmes with the specific goal of preventing severe hypoglycaemia are required. Individuals at high risk need to be monitored with meticulous collection of data on awareness, as well as frequency and severity of all hypoglycaemic episodes.

Faster than the speed of white (noise): potential pressure points in research partnerships and processes

White noise occurs in the thinking, decision making and communication of dominant Settler cultures. It inhibits clear reception of messages, somewhat like the indistinct, fuzzy static of an un-tuned radio. As much a systemic issue as an individual one, it results from assumed privilege and lack of knowledge of worldviews other than the dominant. Until white noise is acknowledged, development of partnerships between Indigenous and non-Indigenous groups is likely to be limited by having to continually start at a point of inequality where nonIndigenous gaps in knowledge and understanding remain unrecognised. This paper/workshop considers challenges encountered while researching experiences of Aboriginal education in Western Australian prisons. Each pressure point occurred where the dominant world view prevailed without question. Discussion will focus on the specific pressure points of ethics approval, project development, informed consent and application of outcomes and findings. The paper asks the questions ‘Who decides what stories are created at these pressure points? What informs those stories?’ As individuals, we might not be able to crash through the white noise barrier but we can chip away and be transparent about its existence with the goal of eventually moving faster than the speed of white (noise).