859 resultados para BORON-CENTERED RADICALS


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Background Epidemiological studies have shown a reduced incidence of cardiovascular disease in the Mediterranean population attributed to the consumption of dietary olive oil rich in antioxidants. This has lead to increased interest in the antioxidant properties of other phenolic compounds of olive tree products. It has been suggested that olive leaf extract may also have health benefits due to its antioxidant and anti-inflammatory activities. Antioxidants can prevent the effects of oxidative metabolism by scavenging free radicals and decreasing the hyperactivity of platelets associated with the development of occlusive thrombosis. No studies to date have investigated the effects of olive leaf extract on platelet function to our knowledge. Improved understanding of the antioxidant properties of olive leaf extract and its effect on platelet function could lead to improved cardiovascular health. Objective The current study used an olive leaf extract prepared from the Olea europaea L. tree. The aim was to determine if polyphenols in olive leaf extract would reduce platelet activity and, to establish an optimal dose in vitro that would reduce platelet aggregation and ATP release. Design Eleven subjects with normal platelet counts (150–400 x 109/L) were recruited for the current in vitro study. Olive leaf extract was added to citrated whole blood to obtain five concentrations ranging from 5.4 ug/mL to 54.0 ug/mL for a dose response curve. Baseline samples, without olive leaf extract were used as a negative control for each subject. After 2 hours incubation with olive leaf extract samples were analyzed for platelet aggregation and ATP release from platelets stimulated by the addition of collagen. Results Whole blood analysis (n=11) showed a clear dose-dependant reduction in platelet aggregation with the increasing olive leaf extract concentrations (p<0.0001). There was also a similar decrease in ATP release from collagen stimulated platelets (p=0.02). Conclusion In the current study the olive leaf extract obtained from Olea europaea L. inhibited platelet aggregation and ATP release from collagen stimulated platelets in vitro. This study suggests olive leaf extract may prevent occlusive thrombosis by reducing platelet hyperactivity.

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The ability of the technique of large-amplitude Fourier transformed (FT) ac voltammetry to facilitate the quantitative evaluation of electrode processes involving electron transfer and catalytically coupled chemical reactions has been evaluated. Predictions derived on the basis of detailed simulations imply that the rate of electron transfer is crucial, as confirmed by studies on the ferrocenemethanol (FcMeOH)-mediated electrocatalytic oxidation of ascorbic acid. Thus, at glassy carbon, gold, and boron-doped diamond electrodes, the introduction of the coupled electrocatalytic reaction, while producing significantly enhanced dc currents, does not affect the ac harmonics. This outcome is as expected if the FcMeOH (0/+) process remains fully reversible in the presence of ascorbic acid. In contrast, the ac harmonic components available from FT-ac voltammetry are predicted to be highly sensitive to the homogeneous kinetics when an electrocatalytic reaction is coupled to a quasi-reversible electron-transfer process. The required quasi-reversible scenario is available at an indium tin oxide electrode. Consequently, reversible potential, heterogeneous charge-transfer rate constant, and charge-transfer coefficient values of 0.19 V vs Ag/AgCl, 0.006 cm s (-1) and 0.55, respectively, along with a second-order homogeneous chemical rate constant of 2500 M (-1) s (-1) for the rate-determining step in the catalytic reaction were determined by comparison of simulated responses and experimental voltammograms derived from the dc and first to fourth ac harmonic components generated at an indium tin oxide electrode. The theoretical concepts derived for large-amplitude FT ac voltammetry are believed to be applicable to a wide range of important solution-based mediated electrocatalytic reactions.

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Gaudefroyite Ca4Mn3+3-x(BO3)3(CO3)(O,OH)3 is an unusual mineral containing both borate and carbonate groups and is found in the oxidation zones of manganese minerals, and it is black in color. Vibrational spectroscopy has been used to explore the molecular structure of gaudefroyite. Gaudefroyite crystals are short dipyramidal or prismatic with prominent pyramidal terminations, to 5 cm. Two very sharp Raman bands at 927 and 1076 cm-1are assigned to trigonal borate and carbonate respectively. Broad Raman bands at 1194, 1219 and 1281 cm-1 are attributed to BOH in-plane bending modes. Raman bands at 649 and 670 cm-1 are assigned to the bending modes of trigonal and tetrahedral boron. Infrared spectroscopy supports these band assignments. Raman bands in the OH stretching region are of a low intensity. The combination of Raman and infrared spectroscopy enables the assessment of the molecular structure of gaudefroyite to be made.

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We have studied the mineral hydroboracite CaMg[B3O4(OH)3]2∙3H2O using electron microscopy and vibrational spectroscopy. Both tetrahedral and trigonal boron units are observed. The nominal resolution of the Raman spectrometer is of the order of 2 cm-1 and as such is sufficient enough to identify separate bands for the stretching bands of the two boron isotopes. The Raman band at 1039 cm-1 is assigned to BO stretching vibration. Raman bands at 1144, 1157, 1229, 1318 cm-1 are attributed to the BOH in-plane bending modes. Raman bands at 825 and 925 cm-1 are attributed to the antisymmetric stretching modes of tetrahedral boron. The sharp Raman peak at 925 cm-1 is from the 11-B component such a mode, then it should have a smaller 10-B satellite near (1.03)x(925) = 952 cm-1, and indeed a small peak at 955 is observed. Four sharp Raman bands observed at 3371, 3507, 3563 and 3632 cm-1 are attributed to the stretching vibrations of hydroxyl units. The broad Raman bands at 3076, 3138, 3255, 3384 and 3551 cm-1 are assigned to water stretching vibrations. Infrared bands at 3367, 3505, 3559 and 3631 cm-1are assigned to the stretching vibration of the hydroxyl units. Broad infrared bands at 3072 and 3254 cm-1 are assigned to water stretching vibrations. Infrared bands at 1318, 1349, 1371, 1383 cm-1 are assigned to the antisymmetric stretching vibrations of trigonal boron

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Tunellite is a strontium borate mineral with formula: SrB6O9(OH)2∙3(H2O) and occurs as colorless crystals in the monoclinic pyramidal crystal system. An intense Raman band at 994 cm-1 was assigned to the BO stretching vibration of the B2O3 units. Raman bands at 1043, 1063, 1082 and 1113 cm-1 are attributed to the in-plane bending vibrations of trigonal boron. Sharp Raman bands observed at 464, 480, 523, 568 and 639 cm-1 are simply defined as trigonal and tetrahedral borate bending modes. The Raman spectrum clearly shows intense Raman bands at 3567 and 3614 cm-1, attributed to OH units. The molecular structure of a natural tunellite has been assessed by using vibrational spectroscopy.

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This study was a phenomenological inquiry of the experience of auditory hallucinations as described by 13 Indonesian people diagnosed with schizophrenia. The interviewees included 6 men and 7 women and they were aged between 19 and 56 years. Four themes emerged from this study: feeling more like a robot than a human being; voices of contradiction - a point of confusion; tattered relationships and family disarray; and normalizing the presence of voices as part of everyday life. The findings of this study have the potential to contribute to new understandings of how people live with and manage auditory hallucinations and so enhance client-centered nursing care.

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Learning science through the process of inquiry is advocated in curriculum documents across many jurisdictions. However, a number of studies suggest that teachers struggle to help students engage in inquiry practices. This is not surprising as many teachers of science have not engaged in scientific inquiry and possibly hold naïve ideas about what constitutes scientific inquiry. This study investigates teachers’ self-reported approaches to teaching science through inquiry. Phenomenographic interviews undertaken with 20 elementary teachers revealed teachers identified six approaches to teaching for inquiry, clustered within three categories. These approaches were categorized as Free and Illustrated Inquiry as part of experience-centered category, Solution and Method Inquiry as part of problem-centered category, and Topic and Chaperoned Inquiry as part of a question-centered category. This study contributes to our theoretical understanding of how teachers approach Inquiry Teaching, and suggests fertile areas of future research into this valued and influential phenomenon broadly known as “Inquiry Teaching”.

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A new method for the direct aryl iodination of isoindolines and isoindoline nitroxides which utilizes periodic acid and potassium iodide in sulfuric acid is presented. Di-iodo functionalized tetramethyl and tetraethyl isoindolines and a di-iodo tetramethyl isoindoline nitroxide were prepared in high yield (70-82%). The analogous mono-iodo species were afforded in modest yield (34-48%). Iodinated nitrones were also obtained from a tetraethyl isoindoline nitroxide.

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We describe a novel and facile approach to covalently graft molecules containing stable free radicals onto carbon surfaces including graphene, carbon nanotubes, glassy carbon and carbon fibres. The new technique employs a stable aryl nitroxide radical diazonium tetrafluoroborate salt. The salt may be isolated and added to carbon surfaces in solution, suspension or electrochemically and represents a convenient, versatile and highly efficient means to adorn graphitic materials with large numbers of free radical spin systems

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Technological advances have led to an influx of affordable hardware that supports sensing, computation and communication. This hardware is increasingly deployed in public and private spaces, tracking and aggregating a wealth of real-time environmental data. Although these technologies are the focus of several research areas, there is a lack of research dealing with the problem of making these capabilities accessible to everyday users. This thesis represents a first step towards developing systems that will allow users to leverage the available infrastructure and create custom tailored solutions. It explores how this notion can be utilized in the context of energy monitoring to improve conventional approaches. The project adopted a user-centered design process to inform the development of a flexible system for real-time data stream composition and visualization. This system features an extensible architecture and defines a unified API for heterogeneous data streams. Rather than displaying the data in a predetermined fashion, it makes this information available as building blocks that can be combined and shared. It is based on the insight that individual users have diverse information needs and presentation preferences. Therefore, it allows users to compose rich information displays, incorporating personally relevant data from an extensive information ecosystem. The prototype was evaluated in an exploratory study to observe its natural use in a real-world setting, gathering empirical usage statistics and conducting semi-structured interviews. The results show that a high degree of customization does not warrant sustained usage. Other factors were identified, yielding recommendations for increasing the impact on energy consumption.

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The goal of this project was to develop a mobile application for the iOS platform, that would support the partner of this project, the Brisbane City Council, in stronger engage citizens in participating in urban planning and development projects. The resulting application is an extended version of FixVegas, a system that allows citizens to report maintenance request to the Brisbane City Council through their smartphone. The new version of the system makes all incoming requests publicly available within the application, allows users to support, comment or disapprove of these. As an addition, the concept of the idea has been introduced. Citizens can submit suggestions for improving the city to the municipality, discuss them with other fellow citizens and, ideally, also with Council representatives. The city officials as well are provided with the ability of publishing development project as an idea and let citizens deliberate it. This way, bidirectional communication between these two parties is created. A web interface complements the iPhone application. The system has been developed after the principle of User Centered Design, by assessing user needs, creating and evaluating prototypes and conducting a user study. The study showed that FixVegas2 has been perceived as an enhancement compared to the previous version, and that the idea concept has been received on a positive note. Indepth questions, such as the influence the system could have on community dynamics or the public participation in urban planning projects could only hardly investigated. However, these findings can be achieved by the alternative study designs that have been proposed.

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Background Breastfeeding self-efficacy (BFSE) supports breastfeeding initiation and duration. Challenges to breastfeeding may undermine BFSE, but second-line strategies including nipple shields, syringe, cup, supply line and bottle feeding may support breastfeeding until challenges are resolved. The primary aim of this study was to examine BFSE in a sample of women using second-line strategies for feeding healthy term infants in the first week postpartum. Methods A retrospective self-report study was conducted using the Breastfeeding Self-Efficacy Scale - Short Form (BSES-SF), demographic and infant feeding questionnaires. Breastfeeding women who gave birth to a singleton healthy term infant at one private metropolitan birthing facility in Australia from November 2008 to February 2009 returned anonymous questionnaires by mail. Results A total of 128 (73 multiparous, 55 primiparous) women participated in the study. The mean BSES-SF score was 51.18 (Standard deviation, SD: 12.48). The median BSES-SF score was 53. Of women using a second-line strategy, 16 exceeded the median, and 42 were below. Analyses using Kruskal-Wallis tests confirmed this difference was statistically significant (H = 21.569, p = 0.001). The rate of second-line strategy use was 48%. The four most commonly used second-line strategies were: bottles with regular teats (77%); syringe feeding (44%); bottles with wide teats (34%); and nipple shields (27%). Seven key challenges were identified that contributed to the decision to use second-line strategies, including: nipple pain (40%); unsettled infant (40%); insufficient milk supply (37%); fatigue (37%); night nursery care (25%); infant weight loss > 10% (24%); and maternal birth associated pain (20%). Skin-to-skin contact at birth was commonly reported (93%). At seven days postpartum 124 women (97%) were continuing to breastfeed. Conclusions The high rate of use of second-line strategies identified in this study and high rate of breastfeeding at day seven despite lower BFSE indicate that such practices should not be overlooked by health professionals. The design of this study does not enable determination of cause-effect relationships to identify factors which contribute to use of second-line strategies. Nevertheless, the significantly lower BSES-SF score of women using a second-line strategy highlights this group of women have particular needs that require attention.

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In most radicals the singly occupied molecular orbital (SOMO) is the highest-energy occupied molecular orbital (HOMO); however, in a small number of reported compounds this is not the case. In the present work we expand significantly the scope of this phenomenon, known as SOMO-HOMO energy-level conversion, by showing that it occurs in virtually any distonic radical anion that contains a sufficiently stabilized radical (aminoxyl, peroxyl, aminyl) non-pi-conjugated with a negative charge (carboxylate, phosphate, sulfate). Moreover, regular orbital order is restored on protonation of the anionic fragment, and hence the orbital configuration can be switched by pH. Most importantly, our theoretical and experimental results reveal a dramatically higher radical stability and proton acidity of such distonic radical anions. Changing radical stability by 3-4 orders of magnitude using pH-induced orbital conversion opens a variety of attractive industrial applications, including pH-switchable nitroxide-mediated polymerization, and it might be exploited in nature.

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Much of what we currently understand about the structure and energetics of multiply charged anions in the gas phase is derived from the measurement of photoelectron spectra of simple dicarboxylate dianions. Here we have employed a modified linear ion-trap mass spectrometer to undertake complementary investigations of the ionic products resulting from laser-initiated electron photodetachment of two model dianions. Electron photodetachment (ePD) of the \[M-2H](2-) dianions formed from glutaric and adipic acid were found to result in a significant loss of ion signal overall, which is consistent with photoelectron studies that report the emission of slow secondary electrons (Xing et al., 2010 \[201). The ePD mass spectra reveal no signals corresponding to the intact \[M-2H](center dot-) radical anions, but rather \[M-2H-CO2](center dot-) ions are identified as the only abundant ionic products indicating that spontaneous decarboxylation follows ejection of the first electron. Interestingly however, investigations of the structure and energetics of the \[M-2H-CO2](center dot-) photoproducts by ion-molecule reaction and electronic structure calculation indicate that (i) these ions are stable with respect to secondary electron detachment and (ii) most of the ion population retains a distonic radical anion structure where the radical remains localised at the position of the departed carboxylate moiety. These observations lead to the conclusion that the mechanism for loss of ion signal involves unimolecular rearrangement reactions of the nascent \[M-2H](center dot-) carbonyloxyl radical anions that compete favourably with direct decarboxylation. Several possible rearrangement pathways that facilitate electron detachment from the radical anion are identified and are computed to be energetically accessible. Such pathways provide an explanation for prior observations of slow secondary electron features in the photoelectron spectra of the same dicaboxylate dianions. (C) 2013 Elsevier B.V. All rights reserved.

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Changes in the molecular structure of polymer antioxidants such as hindered amine light stabilisers (HALS) is central to their efficacy in retarding polymer degradation and therefore requires careful monitoring during their in-service lifetime. The HALS, bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (TIN123) and bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (TIN292), were formulated in different polymer systems and then exposed to various curing and ageing treatments to simulate in-service use. Samples of these coatings were then analysed directly using liquid extraction surface analysis (LESA) coupled with a triple quadrupole mass spectrometer. Analysis of TIN123 formulated in a cross-linked polyester revealed that the polymer matrix protected TIN123 from undergoing extensive thermal degradation that would normally occur at 292 degrees C, specifically, changes at the 1- and 4-positions of the piperidine groups. The effect of thermal versus photo-oxidative degradation was also compared for TIN292 formulated in polyacrylate films by monitoring the in situ conversion of N-CH3 substituted piperidines to N-H. The analysis confirmed that UV light was required for the conversion of N-CH3 moieties to N-H - a major pathway in the antioxidant protection of polymers - whereas this conversion was not observed with thermal degradation. The use of tandem mass spectrometric techniques, including precursor-ion scanning, is shown to be highly sensitive and specific for detecting molecular-level changes in HALS compounds and, when coupled with LESA, able to monitor these changes in situ with speed and reproducibility. (C) 2013 Elsevier B. V. All rights reserved.