979 resultados para radical exchange reactions


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Objective Uterine Papillary Serous Carcinoma (UPSC) is uncommon and accounts for less than 5% of all uterine cancers. Therefore the majority of evidence about the benefits of adjuvant treatment comes from retrospective case series. We conducted a prospective multi-centre non-randomized phase 2 clinical trial using four cycles of adjuvant paclitaxel plus carboplatin chemotherapy followed by pelvic radiotherapy, in order to evaluate the tolerability and safety of this approach. Methods This trial enrolled patients with newly diagnosed, previously untreated patients with stage 1b-4 (FIGO-1988) UPSC with a papillary serous component of at least 30%. Paclitaxel (175 mg/m2) and carboplatin (AUC 6) were administered on day 1 of each 3-week cycle for 4 cycles. Chemotherapy was followed by external beam radiotherapy to the whole pelvis (50.4 Gy over 5.5 weeks). Completion and toxicity of treatment (Common Toxicity Criteria, CTC) and quality of life measures were the primary outcome indicators. Results Twenty-nine of 31 patients completed treatment as planned. Dose reduction was needed in 9 patients (29%), treatment delay in 7 (23%), and treatment cessation in 2 patients (6.5%). Hematologic toxicity, grade 3 or 4 occurred in 19% (6/31) of patients. Patients' self-reported quality of life remained stable throughout treatment. Thirteen of the 29 patients with stages 1–3 disease (44.8%) recurred (average follow up 28.1 months, range 8–60 months). Conclusion This multimodal treatment is feasible, safe and tolerated reasonably well and would be suitable for use in multi-institutional prospective randomized clinical trials incorporating novel therapies in patients with UPSC.

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This article examines the moment of exchange between artist, audience and culture in Live Art. Drawing on historical and contemporary examples, including examples from the Exist in 08 Live Art Event in Brisbane, Australia, in October 2008, it argues that Live Art - be it body art, activist art, site-specific performance, or other sorts of performative intervention in the public sphere - is characterised by a common set of claims about activating audiences, asking them to reflect on cultural norms challenged in the work. Live Art presents risky actions, in a context that blurs the boundaries between art and reality, to position audients as ‘witnesses’ who are personally implicated in, and responsible for, the actions unfolding before them. This article problematises assumptions about the way the uncertainties embedded in the Live Art encounter contribute to its deconstructive agenda. It uses the ethical theory of Emmanuel Levinas, Hans-Thies Lehmann and Dwight Conquergood to examine the mechanics of reductive, culturally-recuperative readings that can limit the efficacy of the Live Art encounter. It argues that, though ‘witnessing’ in Live Art depends on a relation to the real - real people, taking real risks, in real places - if it fails to foreground theatrical frame it is difficult for audients to develop the dual consciousness of the content, and their complicity in that content, that is the starting point for reflexivity, and response-ability, in the ethical encounter.

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Primary aminoporphyrin, secondary bis(porphyrinyl)amine and hydroxyporphyrin complexes have been isolated and characterised both spectroscopically and crystallographically from the reaction of 5-bromo-10,15,20-triphenylporphyrinato-nickel(II) with hydrazine under palladium catalysis.

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Inspired by the initial World Social Forum in Porto Alegre Brazil, over the past decade over 200 local and regional social forums have been held, on five continents. This study has examined the nature of this broader social forum process, in particular as an aspect of the movement for 'another globalisation'. I discuss both the discourses for 'another world', as well as the development of an Alternative Globalisation Movement. As an action research study, the research took place within a variety of groups and networks. The thesis provides six accounts of groups and people striving and struggling for 'another world'. I provide a macro account of the invention and innovation of the World Social Forum. A grassroots film-makers collective provides a window into media. A local social forum opens up the radical diversity of actors. An activist exchange circle sheds light on strategic aspects of alternative globalisation. An educational initiative provides a window into transformations in pedagogy. And a situational account (of the G20 meeting in Melbourne in 2006) provides an overview of the variety of metanetworks that converge to voice demands for global justice and sustainability. In particular, this study has sought to shed light on how, within this process, groups and communities develop 'agency', a capacity to respond to the global challenges they / we face. And as part of this question, I have also explored how alternatives futures are developed and conceived, with a re-cognition of the importance of histories and geo-political (or 'eco-political') structures as contexts. I argue the World Social Forum Process is prefigurative, as an interactional process where many social alternatives are conceived, supported, developed and innovated into the world. And I argue this innovation process is meta-formative, where convergences of diverse actors comprise ‘social ecologies of alternatives’ which lead to opportunities for dynamic collaboration and partnership.

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The contributions of this thesis fall into three areas of certificateless cryptography. The first area is encryption, where we propose new constructions for both identity-based and certificateless cryptography. We construct an n-out-of- n group encryption scheme for identity-based cryptography that does not require any special means to generate the keys of the trusted authorities that are participating. We also introduce a new security definition for chosen ciphertext secure multi-key encryption. We prove that our construction is secure as long as at least one authority is uncompromised, and show that the existing constructions for chosen ciphertext security from identity-based encryption also hold in the group encryption case. We then consider certificateless encryption as the special case of 2-out-of-2 group encryption and give constructions for highly efficient certificateless schemes in the standard model. Among these is the first construction of a lattice-based certificateless encryption scheme. Our next contribution is a highly efficient certificateless key encapsulation mechanism (KEM), that we prove secure in the standard model. We introduce a new way of proving the security of certificateless schemes based that are based on identity-based schemes. We leave the identity-based part of the proof intact, and just extend it to cover the part that is introduced by the certificateless scheme. We show that our construction is more efficient than any instanciation of generic constructions for certificateless key encapsulation in the standard model. The third area where the thesis contributes to the advancement of certificateless cryptography is key agreement. Swanson showed that many certificateless key agreement schemes are insecure if considered in a reasonable security model. We propose the first provably secure certificateless key agreement schemes in the strongest model for certificateless key agreement. We extend Swanson's definition for certificateless key agreement and give more power to the adversary. Our new schemes are secure as long as each party has at least one uncompromised secret. Our first construction is in the random oracle model and gives the adversary slightly more capabilities than our second construction in the standard model. Interestingly, our standard model construction is as efficient as the random oracle model construction.

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We assessed the effect of biochar incorporation into the soil on the soil-atmosphere exchange of the greenhouse gases (GHG) from an intensive subtropical pasture. For this, we measured N2O, CH4 and CO2 emissions with high temporal resolution from April to June 2009 in an existing factorial experiment where cattle feedlot biochar had been applied at 10 t ha-1 in November 2006. Over the whole measurement period, significant emissions of N2O and CO2 were observed, whereas a net uptake of CH4 was measured. N2O emissions were found to be highly episodic with one major emission pulse (up to 502 µg N2O-N m-2 h 1) following heavy rainfall. There was no significant difference in the net flux of GHGs from the biochar amended vs. the control plots. Our results demonstrate that intensively managed subtropical pastures on ferrosols in northern New South Wales of Australia can be a significant source of GHG. Our hypothesis that the application of biochar would lead to a reduction in emissions of GHG from soils was not supported in this field assessment. Additional studies with longer observation periods are needed to clarify the long term effect of biochar amendment on soil microbial processes and the emission of GHGs under field conditions.

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Standardised testing does not recognise the creativity and skills of marginalised youth. This paper presents the development of an innovative approach to assessment designed for the re-engagement of at risk youth who have left formal schooling and are now in an alternative education institution. An electronic portfolio system (EPS) has been developed to capture, record and build on the broad range of students’ cultural and social capital. The assessment as a field of exchange model draws on categories from sociological fields of capital and reconceptualises an eportfolio and social networking hybrid system as a sociocultural zone of learning and development. The EPS, and assessment for learning more generally, are conceptualised as social fields for the exchange of capital (Bourdieu 1977, 1990). The research is underpinned by a sociocultural theoretical perspective that focuses on how students and teachers at the Flexible Learning Centre (FLC) develop and learn, within the zone of proximal development (Vygotsky, 1978). The EPS is seen to be highly effective in the engagement and social interaction between students, teachers and institutions. It is argued throughout this paper that the EPS provides a structurally identifiable space, an arena of social activity, or a field of exchange. The students, teachers and the FLC within this field are producing cultural capital exchanges. The term efield (exchange field) has been coined to refer to this constructed abstract space. Initial results from the trial show a general tendency towards engagement with the EPS and potential for the attainment of socially valued cultural capital in the form of school credentials.

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Thirty-four elementary school teachers and 32 education students from Canada rated their reactions towards vignettes describing children who met attention-deficit/hyperactivity disorder (ADHD) symptom criteria that included or did not include the label “ADHD.” “ADHD”-labeled vignettes elicited greater perceptions of the child's impairment as well as more negative emotions and less confidence in the participants, although it also increased participants' willingness to implement treatment interventions. Ratings were similar to vignettes of boys versus girls; however, important differences in ratings between teachers and education students emerged and are discussed. Finally, we investigated the degree to which teachers' professional backgrounds influenced bias based on the label “ADHD.” Training specific to ADHD consistently predicted label bias, whereas teachers' experience working with children with ADHD did not.

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Discrete stochastic simulations, via techniques such as the Stochastic Simulation Algorithm (SSA) are a powerful tool for understanding the dynamics of chemical kinetics when there are low numbers of certain molecular species. However, an important constraint is the assumption of well-mixedness and homogeneity. In this paper, we show how to use Monte Carlo simulations to estimate an anomalous diffusion parameter that encapsulates the crowdedness of the spatial environment. We then use this parameter to replace the rate constants of bimolecular reactions by a time-dependent power law to produce an SSA valid in cases where anomalous diffusion occurs or the system is not well-mixed (ASSA). Simulations then show that ASSA can successfully predict the temporal dynamics of chemical kinetics in a spatially constrained environment.

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We report the photoinduced conjugation of polymers synthesized via reversible addition−fragmentation chain transfer (RAFT) polymerization with a number of low molecular weight (functional) olefins. Upon irradiation of a solution of an aliphatic alkene and the benzyl dithioacetic acid ester (CPDA) or dodecyl trithiocarbonate (DoPAT) functional poly(alkyl acrylate) at the absorption wavelength of the thiocarbonyl group (315 nm), incorporation of the alkene at the polymer chain-end occurred. The most efficient systems identified with regard to the rate of reaction and yield were poly(butyl acrylate)/CPDA/ethyl vinyl ether (78% monoinsertion product after 1 h) and poly(butyl acrylate)/CPDA/1-pentene (73% insertion product after 7 h) at ambient temperature. An in-depth analysis of the reaction mechanism by 1H NMR and online size-exclusion chromatography-electrospray ionization tandem mass spectrometry (SEC/ESI−MSn) revealed that a possible [2 + 2] photoaddition mechanism of conjugation does not take place. Instead, fast β-cleavage of the photoexcited RAFT-end group with subsequent radical addition of an alkene was observed for all employed systems. The presented reaction thus provides a means of spatial and temporal control for the conjugation of alkenes to thiocarbonyl thio-capped macromolecules via the use of UV radiation.

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In this communication we provide the most recent results on RAFT-mediated ring-closing polymerization of diallyldimethylammonium chloride (DADMAC). The polymerization was carried out in aqueous solution employing 2,2′-azobis(2-methylpropionamidine)-dihydrochloride as the free radical initiator and trithiocarbonate RAFT agent (2-{[(dodecylsulfanyl)carbonothioyl sulfanyl]}propanoic acid, DoPAT) as the controlling RAFT agent. The results show that – while the system is not as completely controlled as previously described – it is nevertheless possible to mediate the polymerization of DADMAC and impart some living characteristics onto the system. The initial study on the RAFT-mediated polymerization of DADMAC may have overestimated the degree of livingness within this reaction. However, it is possible – at low conversions – for some living characteristics to be observed, as the evolution of molecular weight with conversion is linear. In addition, polymers with a reasonably narrow polydispersity can be isolated.

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Intermediaries have introduced electronic services with varying success. One of the problems an intermediary faces is deciding what kind of exchange service it should offer to its customers and suppliers. For example, should it only provide a catalogue or should it also enable customers to order products? Developing the right exchange design is a complex undertaking because of the many design options on the one hand and the interests of multiple actors to be considered on the other. This is far more difficult than simple prescriptions like ‘creating a win-win situation’ suggest. We address this problem by developing design patterns for the exchanges between customers, intermediary, and suppliers related to role, linkage, transparency, and ovelty choices. For developing these design patterns, we studied four distinct electronic intermediaries and dentified exchange design choices that require trade-offs relating to the interests of customers, intermediary, and suppliers. The exchange design patterns contribute to the development of design theory for electronic intermediaries by filling a gap between basic business models and detailed business process designs.