Direct Detection of a Persistent Carbonyloxyl Radical in the Gas Phase

Long lived: Carbonyloxyl radicals (RCO2 .) are reactive intermediates that play key roles in initiating polymerization reactions. This reactivity also makes their direct observation difficult. For the first time a persistent organic RCO2 . radical is detected in the gas phase, its extraordinary longevity is attributed to the high barrier towards fragmentation owing to the endothermicity of the decarboxylation products. Grant Numbers ARC/DP0986738, ARC/DP120102922, ARC/DE120100467

Superoxide does react with peroxides : direct observation of the haber-weiss reaction in the gas phase

The fact that nature provides specific enzymes to selectively remove superoxide (O2.−) from aerobic organisms, namely, the superoxide dismutase enzymes,1 has led to the suggestion that this radical ion may cause the oxidative damage associated with degradative disease and aging.2 Intriguingly, however, superoxide itself is relatively unreactive toward most cellular components, which suggests that dismutase enzymes may ultimately protect the cell against more pernicious oxidants formed from superoxide. As such, there is increasing interest in the endogenous chemistry of superoxide and the pathways by which it might beget more reactive oxygen species. Protonation of superoxide to form the hydroperoxyl radical (HOO.) and dismutation of the same species to hydrogen peroxide (HOOH), with subsequent metal-catalyzed reduction to the hydroxyl radical (HO.), are well-characterized processes in which both the HOO. and HO. radicals are significantly more reactive than their common progenitor.2 Recent examples, however, have also linked superoxide to the putative production of singlet oxygen3 and ozone,4, 5 although the definitive characterization of these chemistries in the cellular milieu has proved challenging

Direct repression of MYB by ZEB1 suppresses proliferation and epithelial gene expression during epithelial-to-mesenchymal transition of breast cancer cells

Introduction Epithelial-to-mesenchymal transition (EMT) promotes cell migration and is important in metastasis. Cellular proliferation is often downregulated during EMT, and the reverse transition (MET) in metastases appears to be required for restoration of proliferation in secondary tumors. We studied the interplay between EMT and proliferation control by MYB in breast cancer cells. Methods MYB, ZEB1, and CDH1 expression levels were manipulated by lentiviral small-hairpin RNA (shRNA)-mediated knockdown/overexpression, and verified with Western blotting, immunocytochemistry, and qRT-PCR. Proliferation was assessed with bromodeoxyuridine pulse labeling and flow cytometry, and sulforhodamine B assays. EMT was induced with epidermal growth factor for 9 days or by exposure to hypoxia (1% oxygen) for up to 5 days, and assessed with qRT-PCR, cell morphology, and colony morphology. Protein expression in human breast cancers was assessed with immunohistochemistry. ZEB1-MYB promoter binding and repression were determined with Chromatin Immunoprecipitation Assay and a luciferase reporter assay, respectively. Student paired t tests, Mann–Whitney, and repeated measures two-way ANOVA tests determined statistical significance (P < 0.05). Results Parental PMC42-ET cells displayed higher expression of ZEB1 and lower expression of MYB than did the PMC42-LA epithelial variant. Knockdown of ZEB1 in PMC42-ET and MDA-MB-231 cells caused increased expression of MYB and a transition to a more epithelial phenotype, which in PMC42-ET cells was coupled with increased proliferation. Indeed, we observed an inverse relation between MYB and ZEB1 expression in two in vitro EMT cell models, in matched human breast tumors and lymph node metastases, and in human breast cancer cell lines. Knockdown of MYB in PMC42-LA cells (MYBsh-LA) led to morphologic changes and protein expression consistent with an EMT. ZEB1 expression was raised in MYBsh-LA cells and significantly repressed in MYB-overexpressing MDA-MB-231 cells, which also showed reduced random migration and a shift from mesenchymal to epithelial colony morphology in two dimensional monolayer cultures. Finally, we detected binding of ZEB1 to MYB promoter in PMC42-ET cells, and ZEB1 overexpression repressed MYB promoter activity. Conclusions This work identifies ZEB1 as a transcriptional repressor of MYB and suggests a reciprocal MYB-ZEB1 repressive relation, providing a mechanism through which proliferation and the epithelial phenotype may be coordinately modulated in breast cancer cells.

Direct observation of the gas phase reaction of the cyclohexyl radical with dioxygen using a distonic radical ion approach

Alkylperoxyl radicals are intermediates in the oxidation Of hydrocarbons. The reactive nature of these intermediates, however, has made therin elusive to direct observation and isolation. We have employed ion trap mass spectrometry to synthesize and characterize 4-carboxylatocyclohexyl radical anions ((center dot)C(6)H(10)-CO(2)(-)) and observe their reactivity in the presence of dioxygen. The resulting reaction is facile (k = 1.8 x 10(-10) cm(3) molecule(-1) s(-1) or 30% of calculated collision rate) and results in (i) the addition Of O(2) to form stabilized 4-carboxylatocyclohexylperoxyl radical anions ((center dot)OO-C(6)H(10)-CO(2)(-)), providing the first direct observation of a cyclohexylperoxyl radical, and (ii) elimination of HO(2)(center dot) and HO(center dot) radicals consistent with recent laser-induced fluorescence studies of the reaction of neutral cyclohexyl radicals with O(2). Electronic structure calculations at the B3LYP/6-31+G(d) level of theory reveal viable pathways for the observed reactions showing that formation of the peroxyl radical is exothermic by 37 kcal mol(-1) with subsequent transition states its low as -6.6 kcal mol(-1) (formation of HO(2)(center dot)) and -9.1 kcal mol(-1) (formation of HO(center dot)) with respect to the entrance channel. The combined computational and experimental data Suggest that the structures of the reaction products correspond to cyclohexenes and epoxides from HO(2)(center dot) and HO(center dot) loss, respectively, while alternative pathways leading to cyclohexanone or ring-opened isomers ate not observed, Activation of the charged peroxyl radical (center dot)OO-C(6)H(10)-CO(2)(-) by collision induced disassociation also results in the loss Of HO(2)(center dot) and HO(center dot) radicals confirming that these products are directly connected to the peroxyl radical intermediate.

Direct integration of battery energy storage systems in distributed power generation

In this paper, a wind energy conversion system interfaced to the grid using a dual inverter is proposed. One of the two inverters in the dual inverter is connected to the rectified output of the wind generator while the other is directly connected to a battery energy storage system (BESS). This approach eliminates the need for an additional dc-dc converter and thus reduces power losses, cost, and complexity. The main issue with this scheme is uncorrelated dynamic changes in dc-link voltages that results in unevenly distributed space vectors. A detailed analysis on the effects of these variations is presented in this paper. Furthermore, a modified modulation technique is proposed to produce undistorted currents even in the presence of unevenly distributed and dynamically changing space vectors. An analysis on the battery charging/discharging process and maximum power point tracking of the wind turbine generator is also presented. Simulation and experimental results are presented to verify the efficacy of the proposed modulation technique and battery charging/discharging process.

Setting aside default judgment - whether applicant must file affidavit providing direct evidence of defence 'on the merits'

In Prus-Butwilowicz v Moxey [2002] QDC 166 the court examined the question whether an applicant for an order setting aside a default judgment was required to file an affidavit providing direct evidence of a defence 'on the merits' and whether the position had changed under the Uniform Civil Procedure Rules 1999 (Qld).

Sport development programmes for Indigenous Australians : innovation, inclusion and development, or a product of ‘white guilt’?

Under the legacy of neoliberalism, it is important to consider how the indigenous people, in this case of Australia, are to advance, develop and achieve some approximation of parity with broader societies in terms of health, educational outcomes and economic participation. In this paper, we explore the relationships between welfare dependency, individualism, responsibility, rights, liberty and the role of the state in the provision of Government-funded programmes of sport to Indigenous communities. We consider whether such programmes are a product of ‘white guilt’ and therefore encourage dependency and weaken the capacity for independence within communities and individuals, or whether programmes to increase rates of participation in sport are better viewed as good investments to bring about changes in physical activity as (albeit a small) part of a broader social policy aimed at reducing the gaps between Indigenous and non-Indigenous Australians in health, education and employment.

Review of direct measurement of inner prosthesis loading in transfemoral amputation: Potential benefits for evidence-based practice

The understanding of the load applied on the residuum through the prosthesis of individuals with transfemoral amputation (TFA) is essential to address a number of concerns that could strongly reduce their quality of life (e.g., residuum skin lesion, prosthesis fitting, alignment). This inner prosthesis loading could be estimated using a typical gait laboratory relying on inverse dynamics equations. Alternative, technological advances proposed over the last decade enabled direct measurement of this kinetic information in a broad variety of situations that could potentially be more relevant in clinical settings. The purposes of this presentation are (A) to review the literature about recent developments in measure and analyses of inner prosthesis loading of TFA, and (B) to extract information that could potentially contribute to a better evidence-based practice.

Direct measurement of prosthetic loading for evidence-based practice

The demand for an evidence-based clinical practice involving lower limb amputees is increasing. Some of the critical care decisions are related to the loading applied on the residuum partially responsible for comfort and functional outcome. This loading can be assessed using inverse dynamics equations. Typically, this method requires a gait laboratory (e.g., 3D motion analysis system, force-plates). It is mainly suited for the analysis only few steps of walking while being expensive and labour intensive. However, recent scientific and industrial developments demonstrated that discrete and light portable sensors can be placed within the prosthesis to measure accurately the loading during an unlimited number of steps and activities of daily living. Several studies indicated that method based on direct measurements might provide more realistic results. Furthermore, it is a user-friendly method more accessible to clinicians, such as prosthetists. The purpose of this symposium will be to give an overview of these additional opportunities for clinicians to obtain relevant data for evidence-based practice. The three main aims will be: • To present some of the equipment used for direct measurements, • To propose ways to analyse some key data sets, • To give some practical example of data sets for transtibial and transfemoral amputees.

Direct mapping of hippocampal surfaces with intrinsic shape context

We propose in this paper a new method for the mapping of hippocampal (HC) surfaces to establish correspondences between points on HC surfaces and enable localized HC shape analysis. A novel geometric feature, the intrinsic shape context, is defined to capture the global characteristics of the HC shapes. Based on this intrinsic feature, an automatic algorithm is developed to detect a set of landmark curves that are stable across population. The direct map between a source and target HC surface is then solved as the minimizer of a harmonic energy function defined on the source surface with landmark constraints. For numerical solutions, we compute the map with the approach of solving partial differential equations on implicit surfaces. The direct mapping method has the following properties: (1) it has the advantage of being automatic; (2) it is invariant to the pose of HC shapes. In our experiments, we apply the direct mapping method to study temporal changes of HC asymmetry in Alzheimer's disease (AD) using HC surfaces from 12 AD patients and 14 normal controls. Our results show that the AD group has a different trend in temporal changes of HC asymmetry than the group of normal controls. We also demonstrate the flexibility of the direct mapping method by applying it to construct spherical maps of HC surfaces. Spherical harmonics (SPHARM) analysis is then applied and it confirms our results on temporal changes of HC asymmetry in AD.

Direct observations of pedestrian unsafe crossing at urban Australian level crossings

The number of pedestrian victims at Australian and foreign level crossings has remained stable over the past decade and it continues to be a significant problem. To examine the factors contributing to pedestrians’ unsafe crossing behaviours, direct observations were conducted at three black spot urban level crossings in Brisbane for a total of 45 h during morning and afternoon peak. In total, 129 pedestrians transgressed the active controls. More transgressions were observed at the crossings located in more populated suburbs in close proximity to large shopping centres and school zones, whereas the smallest number of transgressions were observed at the least populated locations. In addition to characteristics associated with the larger socio-economic area, the patterns of transgression could be associated with the properties of the existing safety equipment and the design of each level crossing (i.e. location of the platforms, number of rail tracks). Indeed, the largest number of crossed unoccupied but “at risk” rail tracks (where a train could have passed), was observed at the crossing with the least transgressions. Contrary to previous findings, younger adults were the most frequent transgressors. School children and elderly were most likely to transgress in groups. Potential directions for future research and more effective measures are discussed.

Pt metal-CeO2 interaction: Direct observation of redox coupling between Pt-0/Pt2+/Pt4+ and Ce4+/Ce3+ states in Ce0.98Pt0.02O2-delta catalyst by a combined electrochemical and x-ray photoelectron spectroscopy study

Pt ions-CeO2 interaction in Ce1-xPtxO2-delta (x=0.02) has been studied for the first time by electrochemical method combined with x-ray diffraction and x-ray photoelectron spectroscopy. Working electrodes made of CeO2 and Ce0.98Pt0.02O2-delta mixed with 30% carbon are treated electrochemically between 0.0-1.2 V in potentiostatic (chronoamperometry) and potentiodynamic (cyclic voltametry) mode with reference to saturated calomel electrode. Reversible oxidation of Pt-0 to Pt2+ and Pt4+ state due to the applied positive potential is coupled to simultaneous reversible reduction of Ce4+ to Ce3+ state. CeO2 reduces to CeO2-y (y=0.35) after applying 1.2 V, which is not reversible; Ce0.98Pt0.02O2-delta reaches a steady state with Pt2+:Pt4+ in the ratio of 0.60:0.40 and Ce4+:Ce3+ in the ratio of 0.55:0.45 giving a composition Ce0.98Pt0.02O1.74 at 1.2 V, which is reversible. Composition of Pt ion substituted compound is reversible between Ce0.98Pt0.02O1.95 to Ce0.98Pt0.02O1.74 within the potential range of 0.0-1.2 V. Thus, Ce0.98Pt0.02O2-delta forms a stable electrode for oxidation of H2O to O-2 unlike CeO2. A linear relation between oxidation of Pt2+ to Pt4+ with simultaneous reduction in Ce4+ to Ce3+ is observed demonstrating Pt-CeO2 metal support interaction is due to reversible Pt-0/Pt2+/Pt4+ interaction with Ce4+/Ce3+ redox couple.

Direct precipitation of lead zirconate titanate by the hydrothermal method

Direct precipitation of fine powders of lead zirconate titanate (PZT) in the complete range of solid solution, is investigated under hydrothermal conditions, starting from lead oxide and titania/zirconia mixed gels. The perovskite phase is formed in the temperature range of 165 – 340°C. Sequence of the hydrothermal reactions is studied by identifying the intermediate phases. The initial formation of PbO: TiO2 solid solution is followed by the reaction of the same with the remaining mixed gels giving rise to X-ray amorphous PZT phase. Further, through crystallite growth, the X-ray crystalline PZT is formed. This method can be extended for the preparation of PLZT powder as well. The resulting powders are sinterable to high density ceramics.

A simple circuit to aid direct measurement of capture cross sections of deep level impurities

An inexpensive and simple circuit to aid the direct measurement of majority carrier capture cross sections of impurity levels in the band gap of a semiconductor by the variable width filling pulse technique is presented. With proper synchronisation, during the period of application of the pulse, the device is disconnected from the capacitance meter to avoid distortion of the pulse and is reconnected again to the meter to record the emission transient. Modes of operation include manual triggering for long emission transients, repetitive triggering for isothermal and DLTS measurements and the DLTS mode which is to be used with signal analysers that already provide a synchronising pulse for disconnection.

New temperature fluctuation method for direct determination of thermal activation energy of deep levels in semiconductors

A new method is suggested where the thermal activation energy is measured directly and not as a slope of an Arrhenius plot. The sample temperature T is allowed to fluctuate about a temperature T0. The reverse-biased sample diode is repeatedly pulsed towards zero bias and the transient capacitance C1 at time t1 is measured The activation energy is obtained by monitoring the fluctuations in C1 and T. The method has been used to measure the activation energy of the gold acceptor level in silicon.