936 resultados para Radical


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The aim os this study is to evaluate and compare the utility of 18F-fluorocholine (18F-CH) PET/CT versus 3-Tesla multiparametric MRI (mpMRI) without endorectal coil to detect tumor recurrences in patients with biochemical relapse following radical prostatectomy (RP). Secondarily, to identify possible prognostic variables associated with mpMRI and 18F-CH PET/CT findings. Retrospective study of 38 patients who developed biochemical recurrence after RP between the years 2011 and 2015 at our institution. PET/CT and mpMRI were both performed within 30 days of each other in all patients. The PET/CT was reviewed by a nuclear medicine specialist while the mpMRI was assessed by a radiologist, both of whom were blinded to outcomes. The median prostate-specific antigen (PSA) value pre-MRI/PET-CT was 0.9 ng/mL (interquartile range 0.4–2.2 ng/mL). There were no differences in the detection rate between 18F-CH PET/CT and mpMRI for local recurrence (LR), lymph node recurrence (LNR) and bone metastases (BM). Separately, mpMRI and 18F-CH PET/CT were positive for recurrence in 55.2% and 52.6% of cases, respectively, and in 65.7% of cases when findings from both modalities were considered together. The detection of LR was better with combined mpMRI and choline PET/CT versus choline PET/CT alone (34.2% vs 18.4%, p = 0.04). Salvage treatment was modified in 22 patients (57.8%) based on the imaging findings. PSA values on the day of biochemical failure were significantly associated with mpMRI positivity (adjusted odds ratio (OR): 30.9; 95% confidence interval (CI): 1.5–635.8). Gleason score > 7 was significantly associated with PET/CT positivity (OR: 13.9; 95% CI: 1.5–125.6). A significant association was found between PSA doubling time (PSADT) (OR: 1.3; 95% CI: 1.0–1.7), T stage (OR: 21.1; 95% CI: 1.6–272.1), and LR. Multiparametric MRI and 18F-CH PET/CT yield similar detection rates for LR, LNR and pelvic BM. The combination of both imaging techniques provides a better LR detection versus choline PET/CT alone. The initially planned salvage treatment was modified in 57.8% of patients due to imaging findings. In addition to PSA values, Gleason score, T stage, and PSADT may provide valuable data to identify those patients that are most likely to benefit from undergoing both imaging procedures.

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As with any new relationship when teachers implement a different or unfamiliar pedagogical approach into the classroom it is often accompanied by a period of unaccustomed behaviour; such as a reluctance for teachers to commit or a wariness from learners to invest or reveal. The challenges that teachers and learners face in the initial stages of this new relationship, if overcome, can be the mainstays of a mutually beneficial learning experience. Yet, as many teachers have experienced, the reverse of this is also true. Failure to adequately invest, plan and commit to the introduction of a new pedagogical approach can bring with it long term consequences that include an unwillingness to ever start a new relationship again.

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BACKGROUND: Functionalized gold nanoparticles are emerging as a promising nanocarrier for target specific delivery of the therapeutic molecules in a cancer cell, as a result it targeted selectively to the cancer cell and minimized the off-target effect. The functionalized nanomaterial (bio conjugate) brings novel functional properties, for example, the high payload of anticancer, antioxidant molecules and selective targeting of the cancer molecular markers. The current study reported the synthesis of multifunctional bioconjugate (GNPs-Pep-A) to target the cancer cell. METHODS: The GNPs-Pep-A conjugate was prepared by functionalization of GNPs with peptide-A (Pro-His-Cys-Lys-Arg-Met; Pep-A) using thioctic acid as a linker molecule. The GNPs-Pep-A was characterized and functional efficacy was tested using Retinoblastoma (RB) cancer model in vitro. RESULTS: The GNPs-Pep-A target the reactive oxygen species (ROS) in RB, Y79, cancer cell more effectively, and bring down the ROS up to 70 % relative to control (untreated cells) in vitro. On the other hand, Pep-A and GNPs showed 40 and 9 % reductions in ROS, respectively, compared to control. The effectiveness of bioconjugate indicates the synergistic effect, due to the coexistence of both organic (Pep-A) and inorganic phase (GNPs) in novel GNPs-Pep-A functional material. In addition to this, it modulates the mRNA expression of antioxidant genes glutathione peroxidase (GPX), superoxide dismutase (SOD) and catalase (CAT) by two-threefolds as observed. CONCLUSIONS: The effects of GNPs-Pep-A on ROS reduction and regulation of antioxidant genes confirmed that Vitis vinifera L. polyphenol-coated GNPs synergistically improve the radical scavenging properties and enhanced the apoptosis of cancer cell.

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Knowledge, Spirit, Law is a de facto phenomenology of scholarship in the age of neoliberal capitalism. The eleven essays (plus Appendices) in Book 1: Radical Scholarship cover topics and circle themes related to the problems and crises specific to neoliberal academia, while proposing creative paths around the various obstructions. The obstructions include metrics-obsessed academia, circular and incestuous peer review, digitalization of research as stalking horse for text- and data-mining, and violation by global corporate fiat of Intellectual Property and the Moral Rights of Authors. These issues, while addressed obliquely in the main text, definitively inform the various proscriptive aspects of the essays and, via the Introduction and Appendices, underscore the necessity of developing new-old means to no obvious end in the production of knowledge — that is to say, a return to forms of non-instrumentalized intellectual inquiry. To be developed in two concurrent volumes, Knowledge, Spirit, Law will serve as a “moving and/or shifting anthology” of new forms of expression in humanistic studies. Book 2: The Anti-Capitalist Sublime will be published in Autumn 2016.

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The infrared (IR) spectroscopic data and Raman spectroscopic properties for a series of 13 “pinwheel-like” homoleptic bis(phthalocyaninato) rare earth complexes M[Pc(α-OC5H11)4]2 [M = Y and Pr–Lu except Pm; H2Pc(α-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected and comparatively studied. Both the IR and Raman spectra for M[Pc(α-OC5H11)4]2 are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues, namely M(Pc)2 and M[Pc(OC8H17)8]2, but resemble (for IR) or are a bit more complicated (for Raman) than those of heteroleptic counterparts M(Pc)[Pc(α-OC5H11)4], revealing the decreased molecular symmetry of these double-decker compounds, namely S8. Except for the obvious splitting of the isoindole breathing band at 1110–1123 cm−1, the IR spectra of M[Pc(α-OC5H11)4]2 are quite similar to those of corresponding M(Pc)[Pc(α-OC5H11)4] and therefore are similarly assigned. With laser excitation at 633 nm, Raman bands derived from isoindole ring and aza stretchings in the range of 1300–1600 cm−1 are selectively intensified. The IR spectra reveal that the frequencies of pyrrole stretching and pyrrole stretching coupled with the symmetrical CH bending of –CH3 groups are sensitive to the rare earth ionic size, while the Raman technique shows that the bands due to the isoindole stretchings and the coupled pyrrole and aza stretchings are similarly affected. Nevertheless, the phthalocyanine monoanion radical Pc′− IR marker band of bis(phthalocyaninato) complexes involving the same rare earth ion is found to shift to lower energy in the order M(Pc)2 > M(Pc)[Pc(α-OC5H11)4] > M[Pc(α-OC5H11)4]2, revealing the weakened π–π interaction between the two phthalocyanine rings in the same order.

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We report a theoretical study of the multiple oxidation states (1+, 0, 1−, and 2−) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3‘,5‘-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the “fully delocalized” or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.

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The synthesis of a new structural class of isoindoline nitroxides (aminoxyls), accessible via the palladium-catalysed Heck reaction, is presented. Reaction of the aryl bromoamine, 5-bromo-1,1,3,3-tetramethylisoindoline (4) or dibromoamine, 5,6-dibromo-1,1,3,3-tetramethylisoindoline (5) or the analogous bromonitroxides 6 and 7 with methyl acrylate gives the acrylate substituted tetramethylisoindoline amines 8 and 10 and nitroxides 12 and 14. Similarly, the reaction of the aryl bromides and dibromides 4–7 with methyl 4-vinylbenzoate gives the carboxystyryl substituted tetramethylisoindoline amines 9 and 11 and the analogous nitroxides 13 and 15. The carboxystyryl tetramethylisoindoline nitroxides demonstrate strongly suppressed fluorescence, which is revealed upon removal of the free radical by reduction or radical coupling.

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This PhD project has expanded the knowledge in the area of profluorescent nitroxides with regard to the synthesis and characterisations of novel profluorescent nitroxide probes as well as physical characterisation of the probe molecules in various polymer/physical environments. The synthesis of the first example of an azaphenalene-based fused aromatic nitroxide TMAO, [1,1,3,3-tetramethyl-2,3-dihydro-2-azaphenalen-2-yloxyl, was described. This novel nitroxide possesses some of the structural rigidity of the isoindoline class of nitroxides, as well as some properties akin to TEMPO nitroxides. Additionally, the integral aromatic ring imparts fluorescence that is switched on by radical scavenging reactions of the nitroxide, which makes it a sensitive probe for polymer degradation. In addition to the parent TMAO, 5 other azaphenalene derivatives were successfully synthesised. This new class of nitroxide was expected to have interesting redox properties when the structure was investigated by high-level ab initio molecular orbitals theory. This was expected to have implications with biological relevance as the calculated redox potentials for the azaphenalene ring class would make them potent antioxidant compounds. The redox potentials of 25 cyclic nitroxides from four different structural classes (pyrroline, piperidine, isoindoline and azaphenalene) were determined by cyclic voltammetry in acetonitrile. It was shown that potentials related to the one electron processes of the nitroxide were influenced by the type of ring system, ring substituents or groups surrounding the moiety. Favourable comparisons were found between theoretical and experimental potentials for pyrroline, piperidine and isoindoline ring classes. Substitution of these ring classes, were correctly calculated to have a small yet predictable effect on the potentials. The redox potentials of the azaphenalene ring class were underestimated by the calculations in all cases by at least a factor of two. This is believed to be due to another process influencing the redox potentials of the azaphenalene ring class which is not taken into account by the theoretical model. It was also possible to demonstrate the use of both azaphenalene and isoindoline nitroxides as additives for monitoring radical mediated damage that occurs in polypropylene as well as in more commercially relevant polyester resins. Polymer sample doped with nitroxide were exposed to both thermo-and photo-oxidative conditions with all nitroxides showing a protective effect. It was found that isoindoline nitroxides were able to indicate radical formation in polypropylene aged at elevated temperatures via fluorescence build-up. The azaphenalene nitroxide TMAO showed no such build-up of fluorescence. This was believed to be due to the more labile bond between the nitroxide and macromolecule and the protection may occur through a classical Denisov cycle, as is expected for commercially available HAS units. Finally, A new profluorescent dinitroxide, BTMIOA (9,10-bis(1,1,3,3- tetramethylisoindolin-2-yloxyl-5-yl)anthracene), was synthesised and shown to be a powerful probe for detecting changes during the initial stages of thermo-oxidative degradation of polypropylene. This probe, which contains a 9,10-diphenylanthracene core linked to two nitroxides, possesses strongly suppressed fluorescence due to quenching by the two nitroxide groups. This molecule also showed the greatest protective effect on thermo-oxidativly aged polypropylene. Most importantly, BTMIOA was found to be a valuable tool for imaging and mapping free-radical generation in polypropylene using fluorescence microscopy.

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Principal topic: Effectuation theory suggests that entrepreneurs develop their new ventures in an iterative way by selecting possibilities through flexibility and interactions with the market; a focus on affordability of loss rather than maximal return on the capital invested, and the development of pre-commitments and alliances from stakeholders (Sarasvathy, 2001, 2008; Sarasvathy et al., 2005, 2006). In contrast, causation may be described as a rationalistic reasoning method to create a company. After a comprehensive market analysis to discover opportunities, the entrepreneur will select the alternative with the higher expected return and implement it through the use of a business plan. However, little is known about the consequences of following either of these two processes. One aspect that remains unclear is the relationship between newness and effectuation. On one hand it can be argued that the combination of a means-centered, interactive (through pre-commitments and alliances with stakeholders from the early phases of the venture creation) and open-minded process (through flexibility of exploiting contingencies) should encourage and facilitate the development of innovative solutions. On the other hand, having a close relationship with their “future first customers” and focussing too much on the resources and knowledge already within the firm may be a constraint that is not conducive to innovation, or at least not to a radical innovation. While it has been suggested that effectuation strategy is more likely to be used by innovative entrepreneurs (Sarasvathy, 2001), this hypothesis has not been demonstrated yet (Sarasvathy, 2001). Method: In our attempt to capture newness in its different aspects we have considered the following four domains where newness may happen: new product/service; new method for promotion and sales; new production methods/sourcing; market creation. We identified how effectuation may be differently associated with these four domains of newness. To test our four sets of hypotheses a dataset of 1329 firms (702 nascent and 627 young firms) randomly selected in Australia was examined through ANOVA Tukey HSD Test. Results and Implications: Results indicate the existence of a curvilinear relationship between effectuation and newness where low and high levels of newness are associated with low level of effectuation while medium level of newness is associated with high level of effectuation. Implications for academia, practitioners and policy makers are also discussed.

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In conventional fabrication of ceramic separation membranes, the particulate sols are applied onto porous supports. Major structural deficiencies under this approach are pin-holes and cracks, and the dramatic losses of flux when pore sizes are reduced to enhance selectivity. We have overcome these structural deficiencies by constructing hierarchically structured separation layer on a porous substrate using lager titanate nanofibers and smaller boehmite nanofibers. This yields a radical change in membrane texture. The resulting membranes effectively filter out species larger than 60 nm at flow rates orders of magnitude greater than conventional membranes. This reveals a new direction in membrane fabrication.

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Information and Communications Technologies globally are moving towards Service Oriented Architectures and Web Services. The healthcare environment is rapidly moving to the use of Service Oriented Architecture/Web Services systems interconnected via this global open Internet. Such moves present major challenges where these structures are not based on highly trusted operating systems. This paper argues the need of a radical re-think of access control in the contemporary healthcare environment in light of modern information system structures, legislative and regulatory requirements, and security operation demands in Health Information Systems. This paper proposes the Open and Trusted Health Information Systems (OTHIS), a viable solution including override capability to the provision of appropriate levels of secure access control for the protection of sensitive health data.

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President’s Report Hello fellow AITPM members, It is interesting to follow the news at present, where transport costs are getting a significant airing. Treasury Secretary Dr Ken Henry has enunciated something Australians may have considered extremely radical just a few years back, but in the present time appears to quite a few to be a realistic alternative. That being a rethink of the way we are charged for using our vehicles. It appears that serious consideration is being given to congestion charging, perhaps in place at least to some extent, of fuel excise. As a transport professional I am pleased that the debate has elevated to the national level, and would look forward that AITPM might contribute appropriately to it. As a motorist though, I naturally have my concerns about being hit in the hip pocket. Not that I actually drive during congested periods very much. I am fortunate to live five minutes either side of two well serviced bus corridors, one of which will eventually become a busway, and work in the central business district, which is hub from all spokes in Brisbane. As such, bus and foot are my preferred commute modes. Ah but I should not gloat, as my smart card fare is about to increase by 20 percent in the New Year! And if the newspapers are to be believed, further substantial increments are proposed over the coming few years. This is reported to recoup some more of the costs of actually providing the quality public transport system that we enjoy in our region. So I expect it will be very interesting to see how transport economics will play out in reality in the coming few years, and how governments cater to Australians who either cannot afford substantial increases in transport costs or have no viable alternatives to those facilities whose costs will increase. The 2010 AITPM National Conference, “What’s New?”, still has the opportunity for authors to submit an abstract for consideration so please consider how you might contribute to the event. Best regards to all, Jon Bunker

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Traditional ceramic separation membranes, which are fabricated by applying colloidal suspensions of metal hydroxides to porous supports, tend to suffer from pinholes and cracks that seriously affect their quality. Other intrinsic problems for these membranes include dramatic losses of flux when the pore sizes are reduced to enhance selectivity and dead-end pores that make no contribution to filtration. In this work, we propose a new strategy for addressing these problems by constructing a hierarchically structured separation layer on a porous substrate using large titanate nanofibers and smaller boehmite nanofibers. The nanofibers are able to divide large voids into smaller ones without forming dead-end pores and with the minimum reduction of the total void volume. The separation layer of nanofibers has a porosity of over 70% of its volume, whereas the separation layer in conventional ceramic membranes has a porosity below 36% and inevitably includes dead-end pores that make no contribution to the flux. This radical change in membrane texture greatly enhances membrane performance. The resulting membranes were able to filter out 95.3% of 60-nm particles from a 0.01 wt % latex while maintaining a relatively high flux of between 800 and 1000 L/m2·h, under a low driving pressure (20 kPa). Such flow rates are orders of magnitude greater than those of conventional membranes with equal selectivity. Moreover, the flux was stable at approximately 800 L/m2·h with a selectivity of more than 95%, even after six repeated runs of filtration and calcination. Use of different supports, either porous glass or porous alumina, had no substantial effect on the performance of the membranes; thus, it is possible to construct the membranes from a variety of supports without compromising functionality. The Darcy equation satisfactorily describes the correlation between the filtration flux and the structural parameters of the new membranes. The assembly of nanofiber meshes to combine high flux with excellent selectivity is an exciting new direction in membrane fabrication.

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INTRODUCTION In their target article, Yuri Hanin and Muza Hanina outlined a novel multidisciplinary approach to performance optimisation for sport psychologists called the Identification-Control-Correction (ICC) programme. According to the authors, this empirically-verified, psycho-pedagogical strategy is designed to improve the quality of coaching and consistency of performance in highly skilled athletes and involves a number of steps including: (i) identifying and increasing self-awareness of ‘optimal’ and ‘non-optimal’ movement patterns for individual athletes; (ii) learning to deliberately control the process of task execution; and iii), correcting habitual and random errors and managing radical changes of movement patterns. Although no specific examples were provided, the ICC programme has apparently been successful in enhancing the performance of Olympic-level athletes. In this commentary, we address what we consider to be some important issues arising from the target article. We specifically focus attention on the contentious topic of optimization in neurobiological movement systems, the role of constraints in shaping emergent movement patterns and the functional role of movement variability in producing stable performance outcomes. In our view, the target article and, indeed, the proposed ICC programme, would benefit from a dynamical systems theoretical backdrop rather than the cognitive scientific approach that appears to be advocated. Although Hanin and Hanina made reference to, and attempted to integrate, constructs typically associated with dynamical systems theoretical accounts of motor control and learning (e.g., Bernstein’s problem, movement variability, etc.), these ideas required more detailed elaboration, which we provide in this commentary.