54 resultados para FIELD-INDUCED OXIDATION
Resumo:
Ever since sodium fluorescein (‘fluorescein’ [FL]) was first used to investigate the ocular surface over a century ago, the term ‘staining’ has been taken to mean the presence of ocular surface fluorescence [1]. This term has not been necessarily taken to infer any particular mechanism of causation, and indeed, can be attributed to a variety of possible aetiologies [2]. In recent times, there has been considerable interest in a form of ocular surface fluorescence seen in association with the use of certain combinations of soft contact lenses and multipurpose solutions. The first clinical account of this phenomenon was reported by Jones et al. [3], which was followed by a more formal investigation by the same author in 2002 [4]. Jones et al described this appearance as a ‘classic solution-based toxicity reaction’. Subsequently, this appearance has come to be known as ‘solution-induced corneal staining’ or more recently by the acronym ‘SICS’ [5]. The term SICS is potentially problematic in that from a cell biology point of view, there is an inference that ‘staining’ means the entry of a dye into corneal epithelial cells. Morgan and Maldonado-Codina [2] noted there was no foundation of solid scientific literature underpinning our understanding of the true basic causative mechanisms of this phenomenon; since that time, further work has been published in this field [6] and [7] but questions still remain about the precise aetiology of this phenomenon...
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The reactions of distonic 4-(N, N, N-trimethylammonium)-2-methylphenyl and 5-(N, N, N-trimethylammonium)-2-methylphenyl radical cations (m/z 149) with O-2 are studied in the gas phase using ion-trap mass spectrometry. Photodissociation (PD) of halogenated precursors gives rise to the target distonic charge-tagged methylphenyl radical whereas collision-induced dissociation (CID) is found to produce unreactive radical ions. The PD generated distonic radicals, however, react rapidly with O-2 to form \[M + O2](center dot+) and \[M + O-2 - OH](center dot+) ions, detected at m/z 181 and m/z 164, respectively. Quantum chemical calculations using G3SX(MP3) and M06-2X theories are deployed to examine key decomposition pathways of the 5-(N, N, N-trimethylammonium)-2-methylphenylperoxyl radical and rationalise the observed product ions. The prevailing product mechanism involves a 1,5- H shift in the peroxyl radical forming a QOOH-type intermediate that subsequently eliminates (OH)-O-center dot to yield charge-tagged 2-quinone methide. Our study suggests that the analogous process should occur for the neutral methylphenyl + O-2 reaction, thus serving as a plausible source of (OH)-O-center dot radicals in combustion environments. Grants: ARC/DP0986738, ARC/DP130100862
Resumo:
The alkaline perhydrolysis of the nerve agent O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) was investigated by studying the ion-molecule reactions of HOO(-) with O,S-dimethyl methylphosphonothioate in a modified linear ion-trap mass spectrometer. In addition to simple proton transfer, two other abundant product ions are observed at m/z 125 and 109 corresponding to the S-methyl methylphosphonothioate and methyl methylphosphonate anions, respectively. The structure of these product ions is demonstrated by a combination of collision-induced dissociation and isotope-labeling experiments that also provide evidence for their formation by nucleophilic reaction pathways, namely, (i) S(N)2 at carbon to yield the S-methyl methylphosphonothioate anion and (ii) nucleophilic addition at phosphorus affording a reactive pentavalent intermediate that readily undergoes internal sulfur oxidation and concomitant elimination of CH(3)SOH to yield the methyl methylphosphonate anion. Consistent with previous Solution phase observations of VX perhydrolysis, the toxic P-O cleavage product is not observed in this VX model system and theoretical calculations identify P-O cleavage to be energetically uncompetitive. Conversely, intramolecular sulfur oxidation is calculated to be extremely exothermic and kinetically accessible explaining its competitiveness with the facile gas phase proton transfer process. Elimination of a sulfur moiety deactivates the nerve agent VX and thus the intramolecular sulfur oxidation process reported here is also able to explain the selective perhydrolysis of the nerve agent to relatively nontoxic products.
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We report a new tuneable alternating current (ac) electrohydrodynamics (ac-EHD) force referred to as “nanoshearing” which involves fluid flow generated within a few nanometers of an electrode surface. This force can be externally tuned via manipulating the applied ac-EHD field strength. The ability to manipulate ac-EHD induced forces and concomitant fluid micromixing can enhance fluid transport within the capture domain of the channel (e.g., transport of analytes and hence increase target–sensor interactions). This also provides a new capability to preferentially select strongly bound analytes over onspecifically bound cells and molecules. To demonstrate the utility and versatility of nanoshearing phenomenon to specifically capture cancer cells, we present proof-of-concept data in lysed blood using two microfluidic devices containing a long array of asymmetric planar electrode pairs. Under the optimal experimental conditions, we achieved high capture efficiency (e.g., approximately 90%; %RSD=2, n=3) with a 10-fold reduction in nonspecific dsorption of non-target cells for the detection of whole cells expressing Human Epidermal Growth Factor Receptor 2 (HER2). We believe that our ac-EHD devices and the use of tuneable nanoshearing phenomenon may find relevance in a wide variety of biological and medical applications.
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Thunderstorm downbursts are important for wind engineers as they have been shown to produce the design wind speeds for mid to high return periods in many regions of Australia [1]. In structural design codes (e.g. AS/NZS1170.02-02) an atmospheric boundary layer (ABL) is assumed, and a vertical profile is interpolated from recorded 10 m wind speeds. The ABL assumption is however inaccurate when considering the complex structure of a thunderstorm outflow, and its effects on engineered structures. Several researchers have shown that the downburst, close to its point of divergence is better represented by an impinging wall jet profile than the traditional ABL. Physical modelling is the generally accepted approach to estimate wind loads on structures and it is therefore important to physically model the thunderstorm downburst so that its effects on engineered structures may be studied. An advancement on the simple impinging jet theory, addressed here is the addition of a pulsing mechanism to the jet which allows not only the divergent characteristics of a downburst to be produced, but also it allows the associated leading ring vortex to be developed. The ring vortex modelling is considered very important for structural design as it is within the horizontal vortex that the largest velocities occur [2]. This paper discusses the flow field produced by a pulsed wall jet, and also discusses the induced pressures that this type of flow has on a scaled tall building.
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Background Artemisinin-combination therapy is a highly effective treatment for uncomplicated falciparum malaria but parasite recrudescence has been commonly reported following artemisinin (ART) monotherapy. The dormancy recovery hypothesis has been proposed to explain this phenomenon, which is different from the slower parasite clearance times reported as the first evidence of the development of ART resistance. Methods In this study, an existing P. falciparum infection model is modified to incorporate the hypothesis of dormancy. Published in vitro data describing the characteristics of dormant parasites is used to explore whether dormancy alone could be responsible for the high recrudescence rates observed in field studies using monotherapy. Several treatment regimens and dormancy rates were simulated to investigate the rate of clinical and parasitological failure following treatment. Results The model output indicates that following a single treatment with ART parasitological and clinical failures occur in up to 77% and 67% of simulations, respectively. These rates rapidly decline with repeated treatment and are sensitive to the assumed dormancy rate. The simulated parasitological and clinical treatment failure rates after 3 and 7 days of treatment are comparable to those reported from several field trials. Conclusions Although further studies are required to confirm dormancy in vivo, this theoretical study adds support for the hypothesis, highlighting the potential role of this parasite sub-population in treatment failure following monotherapy and reinforcing the importance of using ART in combination with other anti-malarials.
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The amount of metal residues from organometallic reagents used in preparation of poly(9,9-dioctylfluorene) by palladium catalysed Suzuki and nickel-induced Yamamoto polycondensations have been determined, and their effect upon the behaviour of the polymer in field-effect transistors (FETs) has been measured. The metal levels from material polymerised by Suzuki method were found to be much higher than from that made by the Yamamoto procedure. Simple treatment of the polymers with suitable metal trapping reagents lowered the metal levels significantly, with EDTA giving best results for nickel and triphenylphosphine for palladium. Comparison of the behaviour of FETs using polyfluorenes with varying levels of metal contamination, showed that the metal residues have little effect upon the mobility values, but often affect the degree of hysteresis, possibly acting as charge traps. Satisfactory device performances were obtained from polymer with palladium levels of 2000 μg/g suggesting that complete removal of metal residues may not be necessary for satisfactory device performance.
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The central dogma in radiation biology is that nuclear DNA is the critical target with respect to radiosensitivity. In accordance with the theoretical expectations, and in the absence of a conclusive model, the general consensus in the field has been to view chromatin as a homogeneous template for DNA damage and repair. This paradigm has been called into question by recent findings indicating a disparity in γ-irradiation-induced γH2AX foci formation in euchromatin and heterochromatin. Here, we have extended those studies and provide evidence that γH2AX foci form preferentially in actively transcribing euchromatin following γ-irradiation.
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Bats have been shown to use information from the Earth's magnetic field during orientation. However, the mechanism underlying this ability remains unknown. In this study we investigated whether bats possess a polarity- or inclination-based compass that could be used in orientation. We monitored the hanging position of adult Nyctalus plancyi in the laboratory in the presence of an induced magnetic field of twice Earth-strength. When under the influence of a normally aligned induced field the bats showed a significant preference for hanging at the northern end of their roosting basket. When the vertical component of the field was reversed, the bats remained at the northern end of the basket. However, when the horizontal component of the field was reversed, the bats changed their positions and hung at the southern end of the basket. Based on these results, we conclude that N. plancyi, unlike all other non-mammalian vertebrates tested to date, uses a polarity-based compass during orientation in the roost, and that the same compass is also likely to underlie bats' long-distance navigation abilities.
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Experimental work could be conducted in either laboratory or at field site. Generally, the laboratory experiments are carried out in an artificial setting and with a highly controlled environment. By contrast, the field experiments often take place in a natural setting, subject to the influences of many uncontrolled factors. Therefore, it is necessary to carefully assess the possible limitations and appropriateness of an experiment before embarking on it. In this paper, a case study of field monitoring of the energy performance of air conditioners is presented. Significant challenges facing the experimental work are described. Lessons learnt from this case study are also discussed. In particular, it was found that on-going analysis of the monitoring data and the correction of abnormal issues are two of the keys for a successful field test program. It was also shown that the installation of monitoring systems could have a significant impact on the accuracy of the data being collected. Before monitoring system was set up to collect monitoring data, it is recommended that an initial analysis of sample monitored data should be conducted to make sure that the monitoring data can achieve the expected precision. In the case where inevitable inherent errors were induced from the installation of field monitoring systems, appropriate remediation may need to be developed and implemented for the improved accuracy of the estimation of results. On-going analysis of monitoring data and correction of any abnormal issues would be the key to a successful field test program.
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Background The benefits associated with some cancer treatments do not come without risk. A serious side effect of some common cancer treatments is cardiotoxicity. Increased recognition of the public health implications of cancer treatment-induced cardiotoxicity has resulted in a proliferation of systematic reviews in this field to guide practice. Quality appraisal of these reviews is likely to limit the influence of biased conclusions from systematic reviews that have used poor methodology related to clinical decision-making. The aim of this meta-review is to appraise and synthesise evidence from only high quality systematic reviews focused on the prevention, detection or management of cancer treatment-induced cardiotoxicity. Methods Using Cochrane methodology, we searched databases, citations and hand-searched bibliographies. Two reviewers independently appraised reviews and extracted findings. A total of 18 high quality systematic reviews were subsequently analysed, 67 % (n = 12) of these comprised meta-analyses. Results One systematic review concluded that there is insufficient evidence regarding the utility of cardiac biomarkers for the detection of cardiotoxicity. The following strategies might reduce the risk of cardiotoxicity: 1) The concomitant administration of dexrazoxane with anthracylines; 2) The avoidance of anthracyclines where possible; 3) The continuous administration of anthracyclines (>6 h) rather than bolus dosing; and 4) The administration of anthracycline derivatives such as epirubicin or liposomal-encapsulated doxorubicin instead of doxorubicin. In terms of management, one review focused on medical interventions for treating anthracycline-induced cardiotoxicity during or after treatment of childhood cancer. Neither intervention (enalapril and phosphocreatine) was associated with statistically significant improvement in ejection fraction or mortality. Conclusion This review highlights the lack of high level evidence to guide clinical decision-making with respect to the detection and management of cancer treatment-associated cardiotoxicity. There is more evidence with respect to the prevention of this adverse effect of cancer treatment. This evidence, however, only applies to anthracycline-based chemotherapy in a predominantly adult population. There is no high-level evidence to guide clinical decision-making regarding the prevention, detection or management of radiation-induced cardiotoxicity.
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Graphitic like layered materials exhibit intriguing electronic structures and thus the search for new types of two-dimensional (2D) monolayer materials is of great interest for developing novel nano-devices. By using density functional theory (DFT) method, here we for the first time investigate the structure, stability, electronic and optical properties of monolayer lead iodide (PbI2). The stability of PbI2 monolayer is first confirmed by phonon dispersion calculation. Compared to the calculation using generalized gradient approximation, screened hybrid functional and spin–orbit coupling effects can not only predicts an accurate bandgap (2.63 eV), but also the correct position of valence and conduction band edges. The biaxial strain can tune its bandgap size in a wide range from 1 eV to 3 eV, which can be understood by the strain induced uniformly change of electric field between Pb and I atomic layer. The calculated imaginary part of the dielectric function of 2D graphene/PbI2 van der Waals type hetero-structure shows significant red shift of absorption edge compared to that of a pure monolayer PbI2. Our findings highlight a new interesting 2D material with potential applications in nanoelectronics and optoelectronics.
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Introduction Markerless motion capture systems are relatively new devices that can significantly speed up capturing full body motion. A precision of the assessment of the finger’s position with this type of equipment was evaluated at 17.30 ± 9.56 mm when compare to an active marker system [1]. The Microsoft Kinect was proposed to standardized and enhanced clinical evaluation of patients with hemiplegic cerebral palsy [2]. Markerless motion capture systems have the potential to be used in a clinical setting for movement analysis, as well as for large cohort research. However, the precision of such system needs to be characterized. Global objectives • To assess the precision within the recording field of the markerless motion capture system Openstage 2 (Organic Motion, NY). • To compare the markerless motion capture system with an optoelectric motion capture system with active markers. Specific objectives • To assess the noise of a static body at 13 different location within the recording field of the markerless motion capture system. • To assess the smallest oscillation detected by the markerless motion capture system. • To assess the difference between both systems regarding the body joint angle measurement. Methods Equipment • OpenStage® 2 (Organic Motion, NY) o Markerless motion capture system o 16 video cameras (acquisition rate : 60Hz) o Recording zone : 4m * 5m * 2.4m (depth * width * height) o Provide position and angle of 23 different body segments • VisualeyezTM VZ4000 (PhoeniX Technologies Incorporated, BC) o Optoelectric motion capture system with active markers o 4 trackers system (total of 12 cameras) o Accuracy : 0.5~0.7mm Protocol & Analysis • Static noise: o Motion recording of an humanoid mannequin was done in 13 different locations o RMSE was calculated for each segment in each location • Smallest oscillation detected: o Small oscillations were induced to the humanoid mannequin and motion was recorded until it stopped. o Correlation between the displacement of the head recorded by both systems was measured. A corresponding magnitude was also measured. • Body joints angle: o Body motion was recorded simultaneously with both systems (left side only). o 6 participants (3 females; 32.7 ± 9.4 years old) • Tasks: Walk, Squat, Shoulder flexion & abduction, Elbow flexion, Wrist extension, Pronation / supination (not in results), Head flexion & rotation (not in results), Leg rotation (not in results), Trunk rotation (not in results) o Several body joint angles were measured with both systems. o RMSE was calculated between signals of both systems. Results Conclusion Results show that the Organic Motion markerless system has the potential to be used for assessment of clinical motor symptoms or motor performances However, the following points should be considered: • Precision of the Openstage system varied within the recording field. • Precision is not constant between limb segments. • The error seems to be higher close to the range of motion extremities.
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Inspired by high porosity, absorbency, wettability and hierarchical ordering on the micrometer and nanometer scale of cotton fabrics, a facile strategy is developed to coat visible light active metal nanostructures of copper and silver on cotton fabric substrates. The fabrication of nanostructured Ag and Cu onto interwoven threads of a cotton fabric by electroless deposition creates metal nanostructures that show a localized surface plasmon resonance (LSPR) effect. The micro/nanoscale hierarchical ordering of the cotton fabrics allows access to catalytically active sites to participate in heterogeneous catalysis with high efficiency. The ability of metals to absorb visible light through LSPR further enhances the catalytic reaction rates under photoexcitation conditions. Understanding the mode of electron transfer during visible light illumination in Ag@Cotton and Cu@Cotton through electrochemical measurements provides mechanistic evidence on the influence of light in promoting electron transfer during heterogeneous catalysis for the first time. The outcomes presented in this work will be helpful in designing new multifunctional fabrics with the ability to absorb visible light and thereby enhance light-activated catalytic processes.