Reaction of Aromatic Peroxyl Radicals with Alkynes: A Mass Spectrometric and Computational Study Using the Distonic Radical Ion Approach

The reaction of the aromatic distonic peroxyl radical cations N-methyl pyridinium-4-peroxyl (PyrOO center dot+) and 4-(N,N,N-trimethyl ammonium)-phenyl peroxyl (AnOO center dot+), with symmetrical dialkyl alkynes 10?ac was studied in the gas phase by mass spectrometry. PyrOO center dot+ and AnOO center dot+ were produced through reaction of the respective distonic aryl radical cations Pyr center dot+ and An center dot+ with oxygen, O2. For the reaction of Pyr center dot+ with O2 an absolute rate coefficient of k1=7.1X10-12 cm3 molecule-1 s-1 and a collision efficiency of 1.2?% was determined at 298 K. The strongly electrophilic PyrOO center dot+ reacts with 3-hexyne and 4-octyne with absolute rate coefficients of khexyne=1.5X10-10 cm3 molecule-1 s-1 and koctyne=2.8X10-10 cm3 molecule-1 s-1, respectively, at 298 K. The reaction of both PyrOO center dot+ and AnOO center dot+ proceeds by radical addition to the alkyne, whereas propargylic hydrogen abstraction was observed as a very minor pathway only in the reactions involving PyrOO center dot+. A major reaction pathway of the vinyl radicals 11 formed upon PyrOO center dot+ addition to the alkynes involves gamma-fragmentation of the peroxy O?O bond and formation of PyrO center dot+. The PyrO center dot+ is rapidly trapped by intermolecular hydrogen abstraction, presumably from a propargylic methylene group in the alkyne. The reaction of the less electrophilic AnOO center dot+ with alkynes is considerably slower and resulted in formation of AnO center dot+ as the only charged product. These findings suggest that electrophilic aromatic peroxyl radicals act as oxygen atom donors, which can be used to generate alpha-oxo carbenes 13 (or isomeric species) from alkynes in a single step. Besides gamma-fragmentation, a number of competing unimolecular dissociative reactions also occur in vinyl radicals 11. The potential energy diagrams of these reactions were explored with density functional theory and ab initio methods, which enabled identification of the chemical structures of the most important products.

A multi-scaling approach to predict hydraulic damage of poromaterials

The purpose of this paper is to introduce the concept of hydraulic damage and its numerical integration. Unlike the common phenomenological continuum damage mechanics approaches, the procedure introduced in this paper relies on mature concepts of homogenization, linear fracture mechanics, and thermodynamics. The model is applied to the problem of fault reactivation within resource reservoirs. The results show that propagation of weaknesses is highly driven by the contrasts of properties in porous media. In particular, it is affected by the fracture toughness of host rocks. Hydraulic damage is diffused when it takes place within extended geological units and localized at interfaces and faults.

Towards an international approach for geography education

"Geography education is indispensable to the development of responsible and active citizens in the present and future world" is one of the main statements in the International Charter on Geographical Education. This charter was edited in 1992 by Haubrich, chair of the Commission on Geographical Education of the International Geographical Union (IGU). Twenty years later this statement is still true. Geography educators all over the world are looking for ways to talk with young people about their image of their world and to help them to develop their knowledge, skills and ideas about the complex world we live in. However, different ideas exist about what geography we should learn and teach and how. The Commission on Geographical Education of the International Geographical Union tries to help to improve the quality and position of geography education worldwide promoting the dissemination of good practices and research results in the field of geography education.

Redrawing the Map : An Interdisciplinary Geocritical Approach to Australian Cultural Narratives

In this chapter we seek to interrogate the methods and assumptions underpinning geocriticism by engaging with and reframing dominant ways of analysing mediated representations of Australian space in cultural narratives, specifically film, literature, and theatre. What, we ask, might geocriticism contribute to the analysis of Australian texts in which location figures prominently? We argue a geocritical approach may provide an interdisciplinary framework that offers a way of identifying tropes across geographic regions and across media representations. Drawing on scholarship spanning Australian cinematic, literary and theatrical narratives, this chapter surveys published work in the field and posits that a refined geocritical mapping and analysis of the cultural terrain foregrounds the significance of geography to culture and draws different traditions of spatial enquiry into dialogue without privileging any particular textual form. We conclude by scoping possibilities for future research emerging from recent technological developments in interactive online cartography.

Deleuze and music : a creative approach to the study of music

The work of Gilles Deleuze has influenced an increasing number of music scholars and practicing musicians, particularly those interested in experimental, electronic and popular music. This is despite the notoriously complex nature of his writings, and the specialised theoretical vocabulary that he employs. This thesis both demystifies some of the key terms and concepts of this vocabulary, before demonstrating how Deleuze’s ideas may be put to work in new and fruitful ways; this is achieved with specific reference to the relationships that music has with thought, time and machines. In Chapter 1, Deleuze’s understanding of the power of thought is examined, in particular his approach to communication, transcendence and immanence, and the “powers of thought.” Each of these concepts helps us to understand Deleuze’s work within broad problem of how to think about music immanently: that is, how to maintain that thought and music are both immanent aspects of life and experience. Chapter 2 examines time within a Deleuzian framework, linking his work on cinema with the concept of the “refrain”; both of these areas prove crucial to his understanding of music, as seen in Deleuze’s approach to the work of Varese, Messiaen, and Boulez. In addition, Deleuze’s understanding of time proves fruitful in examining various aspects of music production, as seen in contemporary electronic dance music. Finally, Chapter 3 looks at the concept of the machine, as developed by Deleuze and Guattari, with reference to the sorts of “machinic” connections that a Deleuzian approach encourages us to seek out in music. Once again, examples from contemporary electronic music are presented, in relation to the notions of becoming and subjectivity. Throughout these chapters, Deleuze’s broad understanding of philosophy as the “creation of concepts” is deployed. This means introducing new ideas and specific types of music that encourage creative and novel engagements with the study of music.

Psychosocial and communication variables involved in mediating the individual experience of older adults following a severe weather event

The recent floods in south-east Queensland have focused policy, academic and community attention on the challenges associated with severe weather events (SWE), specifically pre-disaster preparation, disaster-response and post-disaster community resilience. Financially, the cost of SWE was $9 billion in the 2011 Australian Federal Budget (Swan 2011); psychologically and emotionally, the impact on individual mental health and community wellbeing is also significant but more difficult to quantify. However, recent estimates suggest that as many as one in five will subsequently experience major emotional distress (Bonanno et al. 2010). With climate change predicted to increase the frequency and intensity of a wide range of SWE in Australia (Garnaut 2011; The Climate Institute 2011), there is an urgent and critical need to ensure that the unique psychological and social needs of more vulnerable community members - such as older residents - are better understood and integrated into disaster preparedness and response policy, planning and protocols. Navigating the complex dynamics of SWE can be particularly challenging for older adults and their disaster experience is frequently magnified by a wide array of cumulative and interactive stressors, which intertwine to make them uniquely vulnerable to significant short and long-term adverse effects. This current article provides a brief introduction to the current literature in this area and highlights a gap in the research relating to communication tools during and after severe weather events.

Social Media Analytics : Ein interdisziplinärer Ansatz und seine Implikationen für die Wirtschaftsinformatik [Social Media Analytics - An Interdisciplinary Approach and Its Implications for Information Systems]

Social Media Analytics ist ein neuer Forschungsbereich, in dem interdisziplinäre Methoden kombiniert, erweitert und angepasst werden, um Social-Media-Daten auszuwerten. Neben der Beantwortung von Forschungsfragen ist es ebenfalls ein Ziel, Architekturentwürfe für die Entwicklung neuer Informationssysteme und Anwendungen bereitzustellen, die auf sozialen Medien basieren. Der Beitrag stellt die wichtigsten Aspekte des Bereichs Social Media Analytics vor und verweist auf die Notwendigkeit einer fächerübergreifenden Forschungsagenda, für deren Erstellung und Bearbeitung der Wirtschaftsinformatik eine wichtige Rolle zukommt.

Social media analytics: an interdisciplinary approach and its implications for information systems

Social Media Analytics is an emerging interdisciplinary research field that aims on combining, extending, and adapting methods for analysis of social media data. On the one hand it can support IS and other research disciplines to answer their research questions and on the other hand it helps to provide architectural designs as well as solution frameworks for new social media-based applications and information systems. The authors suggest that IS should contribute to this field and help to develop and process an interdisciplinary research agenda.

A concise approach to the polycyclic scaffold of frondosin D

Frondosins A−E, 1−5 (Figure 1), are a family of related marine sesquiterpenoids first isolated in their dextro-rotatory form from the sponge Dysidea frondosa.(1a) Additionally, levo-rotatory frondosins A and D were isolated from an unidentified Eurospongia species.(1b) Frondosins A−E are compounds of interest due to their promising interleukin-8 (IL-8) affinity and protein kinase C inhibition.(1a) IL-8 antagonists are of particular interest in view of their antiinflammatory,(2a) anti-HIV,(1b, 2b) and antitumor(2c-2f) properties. To date, frondosins A, B, and C have been synthesized.(3) Notwithstanding these successes, the frondosins have proved quite a formidable synthetic challenge, and as of yet, there has been no synthesis of frondosin D or E. In this report, we describe our approaches to the molecular scaffold of frondosins D. This work has culminated in a very effective means of producing the trimethylbicyclo[5.4.0]undecane ring system common to all frondosins (shown in bold, Figure 1).

A new approach to prepare ZVI and its application in removal of Cr(VI) from aqueous solution

Zero valent iron (ZVI) was prepared by reducing natural goethite (NG-ZVI) and synthetic goethite (SG-ZVI) in hydrogen at 550 °C. XRD, TEM, FESEM/EDS and specific surface area (SSA) and pore analyser were used to characterize goethites and reduced goethites. Both NG-ZVI and SG-ZVI with a size of nanoscale to several hundreds of nanometers were obtained by reducing goethites at 550 °C. The reductive capacity of the ZVIs was assessed by removal of Cr(VI) at ambient temperature in comparison with that of commercial iron powder (CIP). The effect of contact time, initial concentration and reaction temperature on Cr(VI) removal was investigated. Furthermore, the uptake mechanism was discussed according to isotherms, thermodynamic analysis and the results of XPS. The results showed that SG-ZVI had the best reductive capacity to Cr(VI) and reduced Cr(VI) to Cr(III). The results suggest that hydrogen reduction is a good approach to prepare ZVI and this type of ZVI is potentially useful in remediating heavy metals as a material of permeable reaction barrier.

The role of the market sub-system and the socio-technical sub-system in innovation and firm performance : a dynamic capabilities approach

Organizational learning has been studied as a key factor in firm performance and internationalization. Moving beyond the past emphasis on market learning, we develop a more complete explanation of learning, its relationship to innovation, and their joint effect on early internationalization. We theorize that, driven by the founders’ international vision, early internationalizing firms employ a dual subsystem of dynamic capabilities: a market subsystem consisting of market-focused learning capability and marketing capability, and a socio-technical subsystem comprised of network learning capability and internally focused learning capability. We argue that innovation mediates the proposed relationship between the dynamic capability structure and early internationalization. We conduct case studies to develop the conceptual framework and test it in a field survey of early internationalizing firms from Australia and the United States. Our findings indicate a complex interplay of capabilities driving innovation and early internationalization. We provide theoretical and practical implications and offer insights for future research.

Quantitative fit analysis of orthopedic bone plates : methods, criteria and approach

Studies on quantitative fit analysis of precontoured fracture fixation plates emerged within the last few years and therefore, there is a wide research gap in this area. Quantitative fit assessment facilitates the measure of the gap between a fracture fixation plate and the underlying bone, and specifies the required plate fit criteria. For clinically meaningful fit assessment outcome, it is necessary to establish the appropriate criteria and parameter. The present paper studies this subject and recommends using multiple fit criteria and the maximum distance between the plate and underlying bone as fit parameter for clinically relevant outcome. We also propose the development of a software tool for automatic plate positioning and fit assessment for the purpose of implant design validation and optimization in an effort to provide better fitting implant that can assist proper fracture healing. The fundamental specifications of the software are discussed.

Fostering rapid transitions to education for sustainable development through a whole-system approach to curriculum and organizational change

Despite decades of attempts to embed sustainability within higher education, literature clearly suggests that highly regulated disciplines such as engineering have been relatively slow to incorporate sustainability knowledge and skill areas, and are generally poorly prepared to do so. With current efforts, it is plausible that sustainability could take another two decades to be embedded within the curriculum. Within this context, this paper presents a whole system approach to implement systematic, intentional and timely curriculum renewal that is responsive to emerging challenges and opportunities, encompassing curriculum and organizational change. The paper begins by considering the evolution of curriculum renewal processes, documenting a number of whole system considerations that have been empirically distilled from literature, case studies, pilot trials, and a series of workshops with built environment educators from around the world over the last decade. The paper outlines a whole-of-institution curriculum renewal approach to embedding sustainability knowledge and skills within the DNA of the institutional offerings. The paper concludes with a discussion of research and practice implications for the field of education research, within and beyond higher education.

A coding approach to the multicast stream authentication problem

We study the multicast stream authentication problem when an opponent can drop, reorder and introduce data packets into the communication channel. In such a model, packet overhead and computing efficiency are two parameters to be taken into account when designing a multicast stream protocol. In this paper, we propose to use two families of erasure codes to deal with this problem, namely, rateless codes and maximum distance separable codes. Our constructions will have the following advantages. First, our packet overhead will be small. Second, the number of signature verifications to be performed at the receiver is O(1). Third, every receiver will be able to recover all the original data packets emitted by the sender despite losses and injection occurred during the transmission of information.