Base-induced decomposition of alkyl hydroperoxides in the gas phase. Part 3. Kinetics and dynamics in HO-+CH3OOH, C2H5OOH, and tert-C4H9OOH reactions

The E-CO(2) elimination reactions of alkyl hydroperoxides proceed via abstraction of an (x-hydrogen by a base: X- + (RRHCOOH)-R-1-H-2 -> HX + (RRC)-R-1-C-2=O + HO-. Efficiencies and product distributions for the reactions of the hydroxide anion with methyl, ethyl, and tert-butyl hydroperoxides are studied in the gas phase. On the basis of experiments using three isotopic analogues, HO- + CH3OOH, HO- + CD3OOH, and H18O- + CH3OOH. the overall intrinsic reaction efficiency is determined to be 80% or greater. The E(CO)2 decomposition is facile for these methylperoxide reactions, and predominates over competing proton transfer at the hydroperoxide moiety. The CH3CH2OOH reaction displays a similar E(CO)2 reactivity, whereas proton transfer and the formation of HOO- are the exclusive pathways observed for (CH3)(3)COOH, which has no (x-hydrogen. All results are consistent with the E-CO(2) mechanism, transition state structure, and reaction energy diagrams calculated using the hybrid density functional B3LYP approach. Isotope labeling for HO- + CH3OOH also reveals some interaction between H2O and HO- within the E(CO)2 product complex [H2O center dot center dot center dot CH2=O center dot center dot center dot HO-]. There is little evidence, however. for the formation of the most exothermic products H2O + CH2(OH)O-, which would arise from nuclephilic condensation of CH2=O and HO-. The results suggest that the product dynamics are not totally statistical but are rather direct after the E-CO(2) transition state. The larger HO- + CH3CH2OOH system displays more statistical behavior during complex dissociation.

Identifying the key sociocultural influences on drinking behavior in high and moderate binge-drinking countries and the public policy implications

Despite considerable state investment and initiatives, binge drinking is still a major behavioral problem for policy makers and communities in many parts of the world. Furthermore, the practice of bingeing on alcohol seems to be spreading to young people in countries traditionally considered to have moderate drinking behaviors. Using a sociocultural lens and a framework of sociocultural themes from previous literature to develop propositions from their empirical study, the authors examine binge-drinking attitudes and behaviors among young people from high and moderate binge-drinking countries. The authors then make proposals regarding how policy makers can use social marketing more effectively to contribute to behavior change. Qualitative interviews were conducted with 91 respondents from 22 countries who were studying in two high binge-drinking countries at the time. The results show support for three contrasting sociocultural propositions that identify influences on binge drinking across these countries.

The activation, appropriation and practices of student-equity policy in Australian higher education

Current national reforms in Australian higher education have prioritised efforts to reduce educational disadvantage within a vernacular expression of neoliberal education policy. Student-equity policy in universities is enmeshed in a set of competitive student recruitment relations. This raises practice-based tensions as universities strive to meet specific institutional targets for low-socio-economic status (SES) and Indigenous student participation, whilst broadening participation more generally within the sector. This paper seeks empirically to trace the activation and appropriation of federal policy through two sites of higher education policy practices: a state government-sponsored equity practitioner body and two differently positioned universities, Dawson and McIllwraith, as they engage with low-SES schools. Working together Dorothy Smith’s insights into the textually mediated activation of local practices, Levinson and colleagues’ concept of the local appropriation of authorised policy, and Bourdieu’s notion of the contested field, we demonstrate that the generation of state level and institutionally specific policies for student-equity practices not only articulates to federal policy, but also appropriates the ruling relations of mandated policy. Further, the scope of these creative local appropriations is organised within a hierarchical academic field through which particular institutional imperatives, as well as the needs of low-SES students, are negotiated. The analysis demonstrates the vernacularisation of policy in the national rearticulation of global discourses, in appropriation at the level of the state body and in the practices of equity workers.

Executive function and postural instability in people with Parkinson’s disease

The specific aspects of cognition contributing to balance and gait have not been clarified in people with Parkinson’s disease (PD). Twenty PD participants and twenty age- and gender-matched healthy controls were assessed on cognition and clinical mobility tests. General cognition was assessed with the Mini Mental State Exam and the Addenbrooke’s Cognitive Exam. Executive function was evaluated using the Trail Making Tests (TMT-A and TMT-B) and a computerized cognitive battery which included a series of choice reaction time (CRT) tests. Clinical gait and balance measures included the Tinetti, Timed Up & Go, Berg Balance and Functional Reach tests. PD participants performed significantly worse than the controls on the tests of cognitive and executive function, balance and gait. PD participants took longer on Trail Making Tests, CRT-Location and CRT-Colour (inhibition response). Furthermore, executive function, particularly longer times on CRT-Distracter and greater errors on the TMT-B were associated with worse balance and gait performance in the PD group. Measures of general cognition were not associated with balance and gait measures in either group. For PD participants, attention and executive function were impaired. Components of executive function, particularly those involving inhibition response and distracters, were associated with poorer balance and gait performance in PD.

Charge transport and density of trap states in balanced high mobility ambipolar organic thin-film transistors

We report on charge transport and density of trap states (trap DOS) in ambipolar diketopyrrolopyrrole-benzothiadiazole copolymer thin-film transistors. This semiconductor possesses high electron and hole field-effect mobilities of up to 0.6 cm 2/V-s. Temperature and gate-bias dependent field-effect mobility measurements are employed to extract the activation energies and trap DOS to understand its unique high mobility balanced ambipolar charge transport properties. The symmetry between the electron and hole transport characteristics, parameters and activation energies is remarkable. We believe that our work is the first charge transport study of an ambipolar organic/polymer based field-effect transistor with room temperature mobility higher than 0.1 cm 2/V-s in both electrons and holes.

A hard slog, not a leap frog : globalization and sustainability transitions in developing Asia

How does globalization influence transitions toward more sustainable socio-technical regimes in the developing world? This paper argues that transformations of regimes, the networks and institutions governing technological and environmental practices in an industry, can be positively influenced by globalization but it depends on how global forces interact with local socio-political landscapes-the political-economic institutions, values, and regulations broadly guiding an economy and its relationship to the environment. We evaluate these relationships through a comparison of two kinds of socio-political landscapes-the neo-liberal export-led development model commonly found in the developing world and the uniquely Asian capitalist developmental state. We first show how the neo-liberal model overemphasizes the power of market forces to facilitate upgrading and more sustainable industrialization. We then argue that capitalist developmental states in East and Southeast Asia have been better able to harness global economic forces for technological and sustainability transitions through an openness to trade and investment and effective public-private institutions able to link cleaner technologies and environmental standards to production activities in firms. We buttress this argument with firm-level evidence showing the evolution of socio-technical regimes in two industries-cement and electronics. The case studies demonstrate how interactions with OECD firms can contribute to environmental technique effects provided the socio-political landscape is amenable to changes in an industry's regime. Ultimately, we find the process of transition to be complex and contingent; a hard slog not a leap frog toward a potentially more sustainable future. We close by considering the limitations on the capitalist developmental state model and with comments about what else needs to be learned about globalization's role in sustainability transitions.

Cross cultural adaptation and validation of a Spanish version of the lower limb functional index

Background: The Lower Limb Functional Index (LLFI) is a relatively recently published regional outcome measure. The development article showed the LLFI had robust and valid clinimetric properties with sound psychometric and practical characteristics when compared to the Lower Limb Extremity Scale (LEFS) criterion standard. Objective: The purpose of this study was cross cultural adaptation and validation of the LLFI Spanish-version (LLFI-Sp) in a Spanish population. Methods: A two stage observational study was conducted. The LLFI was initially cross-culturally adapted to Spanish through double forward and single backward translation; then subsequently validated for the psychometric characteristics of validity, internal consistency, reliability, error score and factor structure. Participants (n = 136) with various lower limb conditions of >12 weeks duration completed the LLFI-Sp, Western Ontario and McMaster University Osteoarthritis Index (WOMAC) and the Euroqol Health Questionnaire 5 Dimensions (EQ-5D-3 L). The full sample was employed to determine internal consistency, concurrent criterion validity, construct validity and factor structure; a subgroup (n = 45) determined reliability at seven days concurrently completing a global rating of change scale. Results: The LLFI-Sp demonstrated high but not excessive internal consistency (α = 0.91) and high reliability (ICC = 0.96). The factor structure was one-dimensional which supported the construct validity. Criterion validity with the WOMAC was strong (r = 0.77) and with the EQ-5D-3 L fair and inversely correlated (r = -0.62). The study limitations included the lack of longitudinal data and the determination of responsiveness. Conclusions: The LLFI-Sp supports the findings of the original English version as being a valid lower limb regional outcome measure. It demonstrated similar psychometric properties for internal consistency, validity, reliability, error score and factor structure.

Cross-cultural adaptation, reliability and validity of the Spanish version of the upper limb functional index

Background The Upper Limb Functional Index (ULFI) is an internationally widely used outcome measure with robust, valid psychometric properties. The purpose of study is to develop and validate a ULFI Spanish-version (ULFI-Sp). Methods A two stage observational study was conducted. The ULFI was cross-culturally adapted to Spanish through double forward and backward translations, the psychometric properties were then validated. Participants (n = 126) with various upper limb conditions of >12 weeks duration completed the ULFI-Sp, QuickDASH and the Euroqol Health Questionnaire 5 Dimensions (EQ-5D-3 L). The full sample determined internal consistency, concurrent criterion validity, construct validity and factor structure; a subgroup (n = 35) determined reliability at seven days. Results The ULFI-Sp demonstrated high internal consistency (α = 0.94) and reliability (r = 0.93). Factor structure was one-dimensional and supported construct validity. Criterion validity with the EQ-5D-3 L was fair and inversely correlated (r = −0.59). The QuickDASH data was unavailable for analysis due to excessive missing responses. Conclusions The ULFI-Sp is a valid upper limb outcome measure with similar psychometric properties to the English language version.

Multiscale features and information extraction of online strain for long-span bridges

The strain data acquired from structural health monitoring (SHM) systems play an important role in the state monitoring and damage identification of bridges. Due to the environmental complexity of civil structures, a better understanding of the actual strain data will help filling the gap between theoretical/laboratorial results and practical application. In the study, the multi-scale features of strain response are first revealed after abundant investigations on the actual data from two typical long-span bridges. Results show that, strain types at the three typical temporal scales of 10^5, 10^2 and 10^0 sec are caused by temperature change, trains and heavy trucks, and have their respective cut-off frequency in the order of 10^-2, 10^-1 and 10^0 Hz. Multi-resolution analysis and wavelet shrinkage are applied for separating and extracting these strain types. During the above process, two methods for determining thresholds are introduced. The excellent ability of wavelet transform on simultaneously time-frequency analysis leads to an effective information extraction. After extraction, the strain data will be compressed at an attractive ratio. This research may contribute to a further understanding of actual strain data of long-span bridges; also, the proposed extracting methodology is applicable on actual SHM systems.

Adaptive estimation of hidden semi-Markov chains with parameterised transition probabilities and exponential decaying states

This paper develops maximum likelihood (ML) estimation schemes for finite-state semi-Markov chains in white Gaussian noise. We assume that the semi-Markov chain is characterised by transition probabilities of known parametric from with unknown parameters. We reformulate this hidden semi-Markov model (HSM) problem in the scalar case as a two-vector homogeneous hidden Markov model (HMM) problem in which the state consist of the signal augmented by the time to last transition. With this reformulation we apply the expectation Maximumisation (EM ) algorithm to obtain ML estimates of the transition probabilities parameters, Markov state levels and noise variance. To demonstrate our proposed schemes, motivated by neuro-biological applications, we use a damped sinusoidal parameterised function for the transition probabilities.

Comparison of the gate drive parameter space for driving power MOSFETs using conventional and cascode configurations

Conventional voltage driven gate drive circuits utilise a resistor to control the switching speed of power MOS-FETs. The gate resistance is adjusted to provide controlled rate of change of load current and voltage. The cascode gate drive configuration has been proposed as an alternative to the conventional resistor-fed gate drive circuit. While cascode drive is broadly understood in the literature the switching characteristics of this topology are not well documented. This paper explores, through both simulation and experimentation, the gate drive parameter space of the cascode gate drive configuration and provides a comparison to the switching characteristics of conventional gate drive.

Poverty by acronym in Australia : welcome to CIM, VIM, PBIM, CPIM and SEAM

This paper discusses Compulsory Income Management (CIM) in Australia and the implications of technology backed forms of surveillance and increasingly conditional benefit payments. The CIM project raises important questions about requiring people to take greater responsibility for their personal behaviour when they no longer have control over key financial aspects of their lives. Some Indigenous communities have resisted the BasicsCard, because CIM was imposed with little prior consultation or subsequent independent evaluation. The compulsory income management of individuals by a paternalist welfare state contradicts and undermines the purported policy aims that they become less welfare dependent and more positively engaged with the world of paid employment and does little to address the growing condition of poverty in Australia.

A Labour of Sex? Male and Female Prostitution

Perspectives in Human Sexuality is an overview of key debates, research findings and theories in the area of sex and sexuality. This textbook written especially for undergraduate students offers a detailed and comprehensive introduction to sex and sexuality from an Australian and New Zealand perspective. It examines controversial issues such as sex and age, sex work and gay, lesbian and queer sex in a fair and balanced manner.

Defining a ‘democratic elite’ : key media in the battle for social responsibility

This paper offers a definition of elite media arguing their content focus will sufficiently meet social responsibility needs of democracy. Its assumptions come from the Finkelstein and Leveson Inquiries and regulatory British Royal Charter (2013). These provide guidelines on how media outlets meet ‘social responsibility’ standards, e.g. press has a ‘responsibility to be fair and accurate’ (Finkelstein); ethical press will feel a responsibility to ‘hold power to account’ (Leveson); news media ‘will be held strictly accountable’ (RC). The paper invokes the British principle of media opting-in to observe standards, and so serve the democracy. It will give examples from existing media, and consider social responsibility of media more generally. Obvious cases of ‘quality’ media: public broadcasters, e.g. BBC, Al-Jazeera, and ‘quality’ press, e.g. NYT, Süddeutscher Zeitung, but also community broadcasters, specialised magazines, news agencies, distinctive web logs, and others. Where providing commentary, these abjure gratuitous opinion -- meeting a standard of reasoned, informational and fair. Funding is almost a definer, many such services supported by the state, private trusts, public institutions or volunteering by staff. Literature supporting discussion on elite media will include their identity as primarily committed to a public good, e.g. the ‘Public Value Test’, Moe and Donders (2011); with reference also to recent literature on developing public service media. Within its limits the paper will treat social media as participants among all media, including elite, and as a parallel dimension of mass communication founded on inter-activity. Elite media will fulfil the need for social responsibility, firstly by providing one space, a ‘plenary’ for debate. Second is the notion of building public recognition of elite media as trustworthy. Third is the fact that elite media together are a large sector with resources to sustain social cohesion and debate; notwithstanding pressure on funds, and impacts of digital transformation undermining employment in media more than in most industries.

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.