68 resultados para 11-CH-12A
Resumo:
Analyzing emotional states under duress or during heightened, life-and-death situations is extremely difficult, especially given the inability of laboratory experiments to replicate the environment and given the inherent biases of post event surveys. This is where natural experiments, such as the pager communications from September 11th can provide the kind of natural experiment emotion researchers have been seeking. We demonstrate that positive and pro-social communications are the first to emerge followed by the slower and lower negative communications. Religious sentiment is the last to emerge, as individual attempt to make sense of event. Additionally we provide a methodological discussion about the preparation and analysis of such natural experiments (the pager message content) and show the importance of using multiple methods to extract the broadest possible understanding.
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IEEE 802.11 based wireless local area networks (WLANs) are being increasingly deployed for soft real-time control applications. However, they do not provide quality-ofservice (QoS) differentiation to meet the requirements of periodic real-time traffic flows, a unique feature of real-time control systems. This problem becomes evident particularly when the network is under congested conditions. Addressing this problem, a media access control (MAC) scheme, QoS-dif, is proposed in this paper to enable QoS differentiation in IEEE 802.11 networks for different types of periodic real-time traffic flows. It extends the IEEE 802.11e Enhanced Distributed Channel Access (EDCA) by introducing a QoS differentiation method to deal with different types of periodic traffic that have different QoS requirements for real-time control applications. The effectiveness of the proposed QoS-dif scheme is demonstrated through comparisons with the IEEE 802.11e EDCA mechanism.
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Vitamin D may have anti-skin cancer effects, but population-based evidence is lacking. We therefore assessed associations between vitamin D status and skin cancer risk in an Australian subtropical community. We analyzed prospective skin cancer incidence for 11 years following baseline assessment of serum 25(OH)-vitamin D in 1,191 adults (average age 54 years) and used multivariable logistic regression analysis to adjust risk estimates for age, sex, detailed assessments of usual time spent outdoors, phenotypic characteristics, and other possible confounders. Participants with serum 25(OH)-vitamin D concentrations above 75 nmol l(-1) versus those below 75 nmol l(-1) more often developed basal cell carcinoma (odds ratio (OR)=1.51 (95% confidence interval (CI): 1.10-2.07, P=0.01) and melanoma (OR=2.71 (95% CI: 0.98-7.48, P=0.05)). Squamous cell carcinoma incidence tended to be lower in persons with serum 25(OH)-vitamin D concentrations above 75 nmol l(-1) compared with those below 75 nmol l(-1) (OR=0.67 (95% CI: 0.44-1.03, P=0.07)). Vitamin D status was not associated with skin cancer incidence when participants were classified as above or below 50 nmol l(-1) 25(OH)-vitamin D. Our findings do not indicate that the carcinogenicity of high sun exposure can be counteracted by high vitamin D status. High sun exposure is to be avoided as a means to achieve high vitamin D status.
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Density functional theory (DFT) calculations have been carried out to explore the catalytic activation of C–H bonds in methane by the iron atom, Fe, and the iron dimer, Fe2. For methane activation on an Fe atom, the calculations suggest that the activation of the first C–H bond is mediated via the triplet excited-state potential energy surface (PES), with initial excitation of Fe to the triplet state being necessary for the reaction to be energetically feasible. Compared with the breaking of the first C–H bond, the cleavage of the second C–H bond is predicted to involve a significantly higher barrier, which could explain experimental observations of the HFeCH3 complex rather than CH2FeH2 in the activation of methane by an Fe atom. For methane activation on an iron dimer, the cleavage of the first C–H bond is quite facile with a barrier only 11.2, 15.8 and 8.4 kcal/mol on the septet state energy surface at the B3LYP/6-311+G(2df,2dp), BPW91/6-311+G(2df,2dp) and M06/B3LYP level, respectively. Cleavage of the second C–H bond from HFe2CH3 involves a barrier calculated respectively as 18.0, 10.7 and 12.4 kcal/mol at the three levels. The results suggest that the elimination of hydrogen from the dihydrogen complex is a rate-determining step. Overall, our results indicate that the iron dimer Fe2 has a stronger catalytic effect on the activation of methane than the iron atom.
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Each year, The Australian Centre for Philanthropy and Nonprofit Studies (CPNS) at Queensland University of Technology (QUT) collects and analyses statistics on the amount and extent of tax-deductible donations made and claimed by Australians in their individual income tax returns to deductible gift recipients (DGRs). The information presented below is based on the amount and type of tax-deductible donations made and claimed by Australian individual taxpayers to DGRs for the period 1 July 2010 to 30 June 2011. This information has been extracted mainly from the Australian Taxation Office's (ATO) publication Taxation Statistics 2010-11. The 2010-11 report is the latest report that has been made publicly available. It represents information in tax returns for the 2010-11 year processed by the ATO as at 31 October 2012.
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Raman and Fourier transform infrared (FT-IR) spectroscopy have been applied to a systematic investigation of the adsorption and decomposition of dichlorodifluoromethane (CCl2F2, CFC-12), fluorotrichloromethane (CCl3F, CFC-11), chlorodifluoromethane (CHClF2, HCFC-22) and molecular chlorine on oxide surfaces. Additionally, the effects of heating and ultraviolet photolysis of the CFC and HCFCs adsorbed on the oxide surfaces have been investigated. Spectral features for these species indicated a small wavenumber shift (1-6 cm-1) associated with the adsorbed phase. Some evidence, specifically the appearance of the Raman band at 507 cm-1, is presented to show that chlorine decomposition species are associated with these oxide surfaces. It was concluded that the new spectral feature (at ca. 507 cm-1) related with the decomposition of the CFC and HCFC molecules was an important indicator of the extent to which the reaction between the adsorbed CFC and HCFC and oxide surface has taken place. The extent of CFC-surface interaction has been quantified in terms of a maximum (Raman) frequency shift parameter (AM). Wavenumber shifts suggest both cation-adsorbate and non-specific adsorption interactions are occurring in the internal channels of the zeolites. Slow decomposition of the adsorbed CFCs under ultraviolet-visible photolysis (at ? > 300 nm) and/or thermal treatment was observed spectroscopically. Using FT-IR spectroscopy, the formation of gas-phase products (CO, CO2, HCl) both onyn photolysis and heating was evident. Results of these measurements are compared with the observed atmospheric reactivity of these compounds.
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Background Matrix metalloproteinases (MMPs) are central to degradation of the extracellular matrix and basement membrane during both normal and carcinogenic tissue remodeling. MT1-MMP (MMP-14) and stromelysin-3 (MMP-11) are two members of the MMP family of proteolytic enzymes that have been specifically implicated in breast cancer progression. Expressed in stromal fibroblasts adjacent to epithelial tumour cells, the mechanism of MT1-MMP and MMP-11 induction remains unknown. Methods To investigate possible mechanisms of induction, we examined the effects of a number of plausible regulatory agents and treatments that may physiologically influence MMP expression during tumour progression. Thus NIH3T3 and primary mouse embryonic fibroblasts (MEFs) were: a) treated with the cytokines IL-1β, IL-2, IL-6, IL-8 and TGF-β for 3, 6, 12, 24, and 48 hours; b) grown on collagens I, IV and V; c) treated with fibronectin, con-A and matrigel; and d) co-cultured with a range of HBC (human breast cancer) cell lines of varied invasive and metastatic potential. Results Competitive quantitative RT-PCR indicated that MMP-11 expression was stimulated to a level greater than 100%, by 48 hour treatments of IL-1β, IL-2, TGF-β, fibronectin and collagen V. No other substantial changes in expression of MMP-11 or MT1-MMP in either tested fibroblast culture, under any treatment conditions, were observed. Conclusion We have demonstrated significant MMP-11 stimulation in mouse fibroblasts using cytokines, matrix constituents and HBC cell lines, and also some inhibition of MT1-MMP. Our data suggest that the regulation of these genes in the complex stromal-epithelial interactions that occur in human breast carcinoma, is influenced by several mechanisms.
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The molecular structure of the arsenate mineral ceruleite has been assessed using a combination of Raman and infrared spectroscopy. The most intense band observed at 903 cm-1 is assigned to the (AsO4)3- symmetric stretching vibrational mode. The infrared spectrum shows intense bands at 787, 827 and 886 cm-1, ascribed to the triply degenerate m3 antisymmetric stretching vibration. Raman bands observed at 373, 400, 417 and 430 cm-1 are attributed to the m2 vibrational mode. Three broad bands for ceruleite found at 3056, 3198 and 3384 cm-1 are assigned to water OH stretching bands. By using a Libowitzky empirical equation, hydrogen bond distances of 2.65 and 2.75 Å are calculated. Vibrational spectra enable the molecular structure of the ceruleite mineral to be determined and whilst similarities exist in the spectral patterns with the roselite mineral group, sufficient differences exist to be able to determine the identification of the minerals.
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This chapter discusses fictional texts set in New York City soon after Septem- ber 11, 2001 (9/11), or whose characters are affected by the attacks on the World Trade Center. Whereas these texts may not have been directly marketed at young adults, they all address ‘youth issues’. Each of the books discussed here contain or are focalized through the eyes of adolescent protagonists. They are all coming-of-age narratives in that the crises within them are usually a result of a catastrophe, taking the characters on journeys of self-discovery, which, once fulfilled, lead them back home.1 As Jerry Griswold (1992) has suggested, coming-of-age stories are especially well suited to the American psyche, and are already familiar to readers of literature based in New York City (the most familiar work being J.D. Salinger’s The Catcher in the Rye). As with other clas- sic American young adult (YA) literature, the journey and homecoming com- monly associated with coming-of-age are often employed in fiction about 9/11. With the key elements of loss and suffering, self-awareness, introspection, and growth, the coming-of-age novel also fulfils agendas common to both litera- ture and politics: the literary journey becomes the nation’s journey.
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Pyrido[1,2-a]benzimidazoles1, 2a are interesting compounds both from the viewpoint of medicinal chemistry2–7 (solubility,7 DNA intercalation3) and materials chemistry8 (fluorescence). Of note among the former is the antibiotic drug Rifaximin,5 which contains this heteroaromatic core. The classical synthetic approach for the assembly of pyrido[1,2-a]benzimidazoles is by [3+3] cyclocondensation of benzimidazoles containing a methylene group at C2 with appropriate bielectrophiles.2a However, these procedures are often low-yielding, involve indirect/lengthy sequences, and/or provide access to a limited range of products, primarily providing derivatives with substituents located on the pyridine ring (A ring, Scheme 1).2–4 Theoretically, a good alternative synthetic method for the synthesis of pyrido[1,2-a]benzimidazoles with substituents in the benzene ring (C ring) should be accessible by intramolecular transition-metal-catalyzed CN bond formation in N-(2-chloroaryl)pyridin-2-amines, based on chemistry recently developed in our research group.9 These substrates themselves are easily available through SNAr or selective Pd-catalyzed amination10 of 2-chloropyridine with 2-chloroanilines.11 If a synthetic procedure that eliminated the need for preactivation of the 2-position of the 2-chloroarylamino entity could be developed, this would be even more powerful, as anilines are more readily commercially available than 2-chloroanilines. Therefore the synthesis of pyrido[1,2-a]benzimidazoles (4) by a transition-metal-catalyzed intramolecular CH amination approach from N-arylpyridin-2-amines (3) was explored (Scheme 1).
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OBJECTIVES: To compare the classification accuracy of previously published RT3 accelerometer cut-points for youth using energy expenditure, measured via portable indirect calorimetry, as a criterion measure. DESIGN: Cross-sectional cross-validation study. METHODS: 100 children (mean age 11.2±2.8 years, 61% male) completed 12 standardized activities trials (3 sedentary, 5 lifestyle and 4 ambulatory) while wearing an RT3 accelerometer. V˙O2 was measured concurrently using the Oxycon Mobile portable calorimeter. Cut-points by Vanhelst (VH), Rowlands (RW), Chu (CH), Kavouras (KV) and the RT3 manufacturer (RT3M) were used to classify PA intensity as sedentary (SED), light (LPA), moderate (MPA) or vigorous (VPA). Classification accuracy was evaluated using the area under the Receiver Operating Characteristic curve (ROC-AUC) and weighted Kappa (κ). RESULTS: For moderate-to-vigorous PA (MVPA), VH, KV and RW exhibited excellent accuracy classification (ROC-AUC≥0.90), while the CH and RT3M exhibited good classification accuracy (ROC-AUC>0.80). Classification accuracy for LPA was fair to poor (ROC-AUC<0.76). For SED, VH exhibited excellent classification accuracy (ROC-AUC>0.90), while RW, CH, and RT3M exhibited good classification accuracy (ROC-AUC>0.80). Kappa statistics ranged from 0.67 (VH) to 0.55 (CH). CONCLUSIONS: All cut-points provided acceptable classification accuracy for SED and MVPA, but limited accuracy for LPA. On the basis of classification accuracy over all four levels of intensity, the use of the VH cut-points is recommended.
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The gas phase degradation reactions of the chemical warfare agent (CWA) simulant, dimethyl methylphosphonate (DMMP), with the hydroperoxide anion (HOO(-)) were investigated using a modified quadrupole ion trap mass spectrometer. The HOO(-) anion reacts readily with neutral DMMP forming two significant product ions at m/z 109 and m/z 123. The major reaction pathways correspond to (i) the nucleophilic substitution at carbon to form \[CH(3)P(O)(OCH(3))O](-) (m/z 109) in a highly exothermic process and (ii) exothermic proton transfer. The branching ratios of the two reaction pathways, 89% and 11% respectively, indicate that the former reaction is significantly faster than the latter. This is in contrast to the trend for the methoxide anion with DMMP, where proton transfer dominates. The difference in the observed reactivities of the HOO(-) and CH(3)O(-) anions can be considered as evidence for an a-effect in the gas phase and is supported by electronic structure calculations at the B3LYP/aug-cc-pVTZ//B3LYP/6-31+G(d) level of theory that indicate the S(N)2(carbon) process has an activation energy 7.8 kJ mol(-1) lower for HOO(-) as compared to CH(3)O(-). A similar alpha-effect was calculated for nucleophilic addition-elimination at phosphorus, but this process an important step in the perhydrolysis degradation of CWAs in solution - was not observed to occur with DMMP in the gas phase. A theoretical investigation revealed that all processes are energetically accessible with negative activation energies. However, comparison of the relative Arrhenius pre-exponential factors indicate that substitution at phosphorus is not kinetically competitive with respect to the S(N)2(carbon) and deprotonation processes.