973 resultados para Hydrogen bond lengths


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Ydinvoimalaitokset on suunniteltu ja rakennettu niin, että niillä on kyky selviytyä erilaisista käyttöhäiriöistä ja onnettomuuksista ilman laitoksen vahingoittumista sekä väestön ja ympäristön vaarantumista. On erittäin epätodennäköistä, että ydinvoimalaitosonnettomuus etenee reaktorisydämen vaurioitumiseen asti, minkä seurauksena sydänmateriaalien hapettuminen voi tuottaa vetyä. Jäädytyspiirin rikkoutumisen myötä vety saattaa kulkeutua ydinvoimalaitoksen suojarakennukseen, jossa se voi muodostaa palavan seoksen ilman hapen kanssa ja palaa tai jopa räjähtää. Vetypalosta aiheutuvat lämpötila- ja painekuormitukset vaarantavat suojarakennuksen eheyden ja suojarakennuksen sisällä olevien turvajärjestelmien toimivuuden, joten tehokas ja luotettava vedynhallintajärjestelmä on tarpeellinen. Passiivisia autokatalyyttisiä vetyrekombinaattoreita käytetäänyhä useammissa Euroopan ydinvoimaitoksissa vedynhallintaan. Nämä rekombinaattorit poistavat vetyä katalyyttisellä reaktiolla vedyn reagoidessa katalyytin pinnalla hapen kanssa muodostaen vesihöyryä. Rekombinaattorit ovat täysin passiivisiaeivätkä tarvitse ulkoista energiaa tai operaattoritoimintaa käynnistyäkseen taitoimiakseen. Rekombinaattoreiden käyttäytymisen tutkimisellatähdätään niiden toimivuuden selvittämiseen kaikissa mahdollisissa onnettomuustilanteissa, niiden suunnittelun optimoimiseen sekä niiden optimaalisen lukumäärän ja sijainnin määrittämiseen suojarakennuksessa. Suojarakennuksen mallintamiseen käytetään joko keskiarvoistavia ohjelmia (Lumped parameter (LP) code), moniulotteisia virtausmalliohjelmia (Computational Fluid Dynamics, CFD) tai näiden yhdistelmiä. Rekombinaattoreiden mallintaminen on toteutettu näissä ohjelmissa joko kokeellisella, teoreettisella tai yleisellä (eng. Global Approach) mallilla. Tämä diplomityö sisältää tulokset TONUS OD-ohjelman sisältämän Siemens FR90/1-150 rekombinaattorin mallin vedynkulutuksen tarkistuslaskuista ja TONUS OD-ohjelmalla suoritettujen laskujen tulokset Siemens rekombinaattoreiden vuorovaikutuksista. TONUS on CEA:n (Commissariat à 1'En¬ergie Atomique) kehittämä LP (OD) ja CFD -vetyanalyysiohjelma, jota käytetään vedyn jakautumisen, palamisenja detonaation mallintamiseen. TONUS:sta käytetään myös vedynpoiston mallintamiseen passiivisilla autokatalyyttisillä rekombinaattoreilla. Vedynkulutukseen vaikuttavat tekijät eroteltiin ja tutkittiin yksi kerrallaan. Rekombinaattoreiden vuorovaikutuksia tutkittaessa samaan tilavuuteen sijoitettiin eri kokoisia ja eri lukumäärä rekombinaattoreita. Siemens rekombinaattorimalli TONUS OD-ohjelmassa laskee vedynkulutuksen kuten oletettiin ja tulokset vahvistavat TONUS OD-ohjelman fysikaalisen laskennan luotettavuuden. Mahdollisia paikallisia jakautumia tutkitussa tilavuudessa ei voitu havaita LP-ohjelmalla, koska se käyttäälaskennassa suureiden tilavuuskeskiarvoja. Paikallisten jakautumien tutkintaan tarvitaan CFD -laskentaohjelma.

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Objectives: To evaluate the shear bond strength and site of failure of brackets bonded to dry and wet enamel. Study design: 50 teeth were divided into ten groups of 5 teeth each (10 surfaces). In half the groups enamel was kept dry before bonding, and in the other half distilled water was applied to wet the surface after etching. The following groups were established: 1)Acid/Transbond-XT (dry/wet) XT; 2) Transbond Plus Self Etching Primer (TSEP)/Transbond-XT paste (dry/wet); 3) Concise (dry), Transbond MIP/Concise (wet), 4) FujiOrtho-LC (dry/wet); 5) SmartBond (dry/wet). Brackets were bonded to both buccal and lingual surfaces. Specimens were stored in distilled water (24 hours at 37ºC) and thermocycled. Brackets were debonded using a Universal testing machine (cross-head speed 1 mm/min). Failure sites were classified using a stereomicroscope. Results: No significant differences in bond strength were detected between the adhesives under wet and dry conditions except for Smart- Bond, whose bond strength was significantly lower under dry conditions. For all the adhesives most bond failures were of mixed site location except for Smartbond, which failed at the adhesive-bracket interface. Conclusions: Under wet conditions the bonding capacity of the adhesives tested was similar than under dry conditions, with the exception of SmartBond which improved under wet conditions

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BACKGROUND: While rifaximin was able to improve symptoms in patients with irritable bowel syndrome (IBS) in phase III trials, these results are yet to be repeated in phase IV studies. AIM: To evaluate the treatment response to rifaximin in IBS patients in a phase IV trial. METHODS: IBS patients underwent lactulose hydrogen breath testing (LHBT). LHBT-positive patients were treated with rifaximin for 14 days. Prior to treatment as well as at week 4 and 14 following the start of rifaximin treatment, patients completed a questionnaire assessing symptom severity on a Likert scale from 0 to 10. RESULTS: One hundred and six of 150 IBS patients (71%) were LHBT-positive and treated with rifaximin. As assessed at week 4 following commencement of the therapy, rifaximin provided significant improvement of the following IBS-associated symptoms: bloating (5.5±2.6 before the start of the treatment vs. 3.6±2.7 at week 4, P<0.001), flatulence (5.0±2.7 vs. 4.0±2.7, P=0.015), diarrhoea (2.9±2.4 vs. 2.0±2.4, P=0.005) and abdominal pain (4.8±2.7 vs. 3.3±2.5, P<0.001). Overall well-being also significantly improved (3.9 ± 2.4 vs. 2.7 ± 2.3, P < 0.001). Similar improvements in IBS symptoms were obtained at week 14. Eighty-six per cent of patients undergoing repetitive LHBT (55/64) tested negative at week 4. CONCLUSIONS: We found a high percentage of LHBT-positive IBS patients. IBS-associated symptoms (bloating, flatulence, diarrhoea, pain) were improved for a period of 3 months following 2 weeks of treatment with rifaximin. We conclude that rifaximin treatment alleviates symptoms in LHBT-positive IBS patients.

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OBJECTIVE: To evaluate the variability of bond strength test results of adhesive systems (AS) and to correlate the results with clinical parameters of clinical studies investigating cervical restorations. MATERIALS AND METHODS: Regarding the clinical studies, the internal database which had previously been used for a meta-analysis on cervical restorations was updated with clinical studies published between 2008 and 2012 by searching the PubMed and SCOPUS databases. PubMed and the International Association for Dental Research abstracts online were searched for laboratory studies on microtensile, macrotensile and macroshear bond strength tests. The inclusion criteria were (1) dentin, (2) testing of at least four adhesive systems, (3) same diameter of composite and (4) 24h of water storage prior to testing. The clinical outcome variables were retention loss, marginal discoloration, detectable margins, and a clinical index comprising the three parameters by weighing them. Linear mixed models which included a random study effect were calculated for both, the laboratory and the clinical studies. The variability was assessed by calculating a ratio of variances, dividing the variance among the estimated bonding effects obtained in the linear mixed models by the sum of all variance components estimated in these models. RESULTS: Thirty-two laboratory studies fulfilled the inclusion criteria comprising 183 experiments. Of those, 86 used the microtensile test evaluating 22 adhesive systems (AS). Twenty-seven used the macrotensile test with 17 AS, and 70 used the macroshear test with 24 AS. For 28 AS the results from clinical studies were available. Microtensile and macrotensile (Spearman rho=0.66, p=0.007) were moderately correlated and also microtensile and macroshear (Spearman rho=0.51, p=0.03) but not macroshear and macrotensile (Spearman rho=0.34, p=0.22). The effect of the adhesive system was significant for microtensile and macroshear (p<0.001) but not for macrotensile. The effect of the adhesive system could explain 36% of the variability of the microtensile test, 27% of the macrotensile and 33% of the macroshear test. For the clinical trials, about 49% of the variability of retained restorations could be explained by the adhesive system. With respect to the correlation between bond strength tests and clinical parameters, only a moderate correlation between micro- and macrotensile test results and marginal discoloration was demonstrated. However, no correlation between these tests and a retention loss or marginal integrity was shown. The correlation improved when more studies were included compared to assessing only one study. SIGNIFICANCE: The high variability of bond strength test results highlights the need to establish individual acceptance levels for a given test institute. The weak correlation of bond-strength test results with clinical parameters leads to the conclusion that one should not rely solely on bond strength tests to predict the clinical performance of an adhesive system but one should conduct other laboratory tests like tests on the marginal adaptation of fillings in extracted teeth and the retention loss of restorations in non-retentive cavities after artificial aging.

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The structural relaxation of pure amorphous silicon a-Si and hydrogenated amorphous silicon a-Si:H materials, that occurs during thermal annealing experiments, has been analyzed by Raman spectroscopy and differential scanning calorimetry. Unlike a-Si, the heat evolved from a-Si:H cannot be explained by relaxation of the Si-Si network strain but it reveals a derelaxation of the bond angle strain. Since the state of relaxation after annealing is very similar for pure and hydrogenated materials, our results give strong experimental support to the predicted configurational gap between a-Si and crystalline silicon.

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Oxidative stress is implicated in the pathogenesis of neurodegenerative disorders and hydrogen peroxide (H2O2) plays a central role in the stress. Huprines, a group of potent acetylcholinesterase inhibitors (AChEIs), have shown a broad cholinergic pharmacological profile. Recently, it has been observed that huprine X (HX) improves cognition in non transgenic middle aged mice and shows a neuroprotective activity (increased synaptophysin expression) in 3xTg-AD mice. Consequently, in the present experiments the potential neuroprotective effect of huprines (HX, HY, HZ) has been analyzed in two different in vitro conditions: undifferentiated and NGF-differentiated PC12 cells. Cells were subjected to oxidative insult (H2O2, 200 µM) and the protective effects of HX, HY and HZ (0.01 µM- 1 µM) were analyzed after a pre-incubation period of 24 and 48 hours. All huprines showed protective effects in both undifferentiated and NGF-differentiated cells, however only in differentiated cells the effect was dependent on cholinergic receptors as atropine (muscarinic antagonist, 0.1 µM) and mecamylamine (nicotinic antagonist, 100 µM) reverted the neuroprotection action of huprines. The decrease in SOD activity observed after oxidative insult was overcome in the presence of huprines and this effect was not mediated by muscarinic or nicotinic receptors. In conclusion, huprines displayed neuroprotective properties as previously observed in in vivo studies. In addition, these effects were mediated by cholinergic receptors only in differentiated cells. However, a non-cholinergic mechanism, probably through an increase in SOD activity, seems to be also involved in the neuroprotective effects of huprines.

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Aquaporins are water channel proteins that mediate the fine-tuning of cell membrane water permeability during development or in response to environmental stresses. The present work focuses on the oxidative stress-induced redistribution of plasma membrane intrinsic protein (PIP) aquaporins from the plasma membrane (PM) to intracellular membranes. This process was investigated in the Arabidopsis root. Sucrose density gradient centrifugation showed that exposure of roots to 0.5 mM H2O2 induces significant depletion in PM fractions of several abundant PIP homologs after 15 min. Analyses by single-particle tracking and fluorescence correlative spectroscopy showed that, in the PM of epidermal cells, H2O2 treatment induces an increase in lateral motion and a reduction in the density of a fluorescently tagged form of the prototypal AtPIP2;1 isoform, respectively. Co-expression analyses of AtPIP2;1 with endomembrane markers revealed that H2O2 triggers AtPIP2;1 accumulation in the late endosomal compartments. Life-time analyses established that the high stability of PIPs was maintained under oxidative stress conditions, suggesting that H2O2 triggers a mechanism for intracellular sequestration of PM aquaporins without further degradation. In addition to information on cellular regulation of aquaporins, this study provides novel and complementary insights into the dynamic remodeling of plant internal membranes during oxidative stress responses.

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Minimizing the risks of an investment portfolio but not in the favour of expected returns is one of the key interests of an investor. Typically, portfolio diversification is achieved using two main strategies: investing in different classes of assets thought to have little or negative correlations or investing in similar classes of assets in multiple markets through international diversification. This study investigates integration of the Russian financial markets in the time period of January 1, 2003 to December 28, 2007 using daily data. The aim is to test the intra-country and cross-country integration of the Russian stock and bond markets between seven countries. Our test methodology for the short-run dynamics testing is the vector autoregressive model (VAR) and for the long-run cointegration testing we use the Johansen cointegration test which is an extension to VAR. The empirical results of this study show that the Russian stock and bond markets are not integrated in the long-run either at intra-country or cross-country level which means that the markets are relatively segmented. The short-run dynamics are also relatively low. This implies a presence of potential gains from diversification.

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L'hydrogène sulfuré (H2S) est un gaz toxique retrouvé à l'état naturel et dans certains milieux industriels, à l'origine d'intoxication accidentelle, mais pouvant être également et facilement synthétisé de manière domestique. Des cas de suicide par hydrogène sulfuré ont ainsi été décrits à partir de produits ménagers dans la littérature depuis 2009, aux États-Unis et au Japon. La plupart présentait des délais post mortem (DPM) courts (moins de 72 heures). En France, les intoxications aiguës à l'H2S demeurent rares et sont le plus souvent liées à des accidents du travail. Nous rapportons ici le cas d'un homme âgé de 37 ans découvert à son domicile, en état de décomposition avancée avec un DPM de deux mois. Compte tenu de la présence d'une importante signalétique avisant du danger potentiel d'exposition à l'H2S, des mesures de précaution ont été mises en oeuvre dès la découverte du corps et poursuivies jusqu'aux opérations d'autopsie. Les analyses toxicologiques ont confirmé la présence d'H2S au niveau des prélèvements de cerveau et de muscle. Le cas présenté constitue le premier cas de suicide avec un délai post mortem long à l'H2S rapporté en France. Dans la littérature, les constatations macroscopiques à l'autopsie ne sont pas spécifiques tandis que les analyses toxicologiques reposent essentiellement sur la recherche et la quantification d'H2S. En raison de leur redistribution post mortem, les résultats de ces analyses doivent être interprétés avec prudence, et encore plus en cas de délai post mortem long et de phénomènes de putréfaction qui peuvent également être une source de génération d'H2S post mortem. Hydrogen sulfide (H2S) which is a poisonous gas found either in the natural state or in industrial environments and potentially linked with accidental intoxication, can also be easily handmade. Several cases of suicide by inhaling H2S produced by mixing household products have been reported in the literature since 2009 in USA and Japan. Most of them involved short post mortem delays up to 72 hours. In France, acute H2S poisoning remains rare and mostly accidental. We report the case of a 37-year-old man found at home, in an advanced stage of decomposition with a 2-month post mortem delay. As numerous warning signs about a high risk of H2S exposure were present, some precautionary measures were taken from the discovery of the cadaver to the autopsy. Toxicological analyses confirmed the presence of H2S in brain and muscle samples. This observation is the first French case with a long post mortem delay. As macroscopic findings in such cases are described to be unspecific in literature, toxicological analysis must focus on the detection and the quantification of H2S. However, due to the phenomena of post mortem drug redistribution and neo-formation, their results should be interpreted with much more caution when the post mortem delay is long. The potential increase in such voluntary-intoxication-related-deaths in France, similar to the recent Japanese and American waves of suicides, requires for forensic scientists, a good knowledge of both thanatological and toxicological pictures, and precautionary measures to adopt in such situations.

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Prediction of the stock market valuation is a common interest to all market participants. Theoretically sound market valuation can be achieved by discounting future earnings of equities to present. Competing valuation models seek to find variables that affect the equity market valuation in a way that the market valuation can be explained and also variables that could be used to predict market valuation. In this paper we test the contemporaneous relationship between stock prices, forward looking earnings and long-term government bond yields. We test this so-called Fed model in a long- and short-term time series analysis. In order to test the dynamics of the relationship, we use the cointegration framework. The data used in this study spans over four decades of various market conditions between 1964-2007, using data from United States. The empirical results of our analysis do not give support for the Fed model. We are able to show that the long-term government bonds do not play statistically significant role in this relationship. The effect of forward earnings yield on the stock market prices is significant and thus we suggest the use of standard valuation ratios when trying to predict the future paths of equity prices. Also, changes in the long-term government bond yields do not have significant short-term impact on stock prices.

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In this work is presented and tested (for 106 adducts, mainly of the zinc group halides) two empirical equations supported in TG data to estimate the value of the metal-ligand bond dissociation enthalpy for adducts: <D> (M-O) = t i / g if t i < 420 K and <D> (M-O) = (t i / g ) - 7,75 . 10-2 . t i if t i > 420 K. In this empirical equations, t i is the thermodynamic temperature of the beginning of the thermal decomposition of the adduct, as determined by thermogravimetry, andg is a constant factor that is function of the metal halide considered and of the number of ligands, but is not dependant of the ligand itself. To half of the tested adducts the difference between experimental and calculated values was less than 5%. To about 80% of the tested adducts, the difference between the experimental (calorimetric) and the calculated (using the proposed equations) values are less than 15%.

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The present study reports details of the stoichiometric characterization of the mixed complex system, V(H2O2)PAR, formed when vanadium adequately reacts with hydrogen peroxide and with 4-(2-Pyridilazo)Resorcinol. Also the presence of polynuclear species was investigated in order to elucidate about unambiguous assignment of the molar absorptivity, stability constant and composition of the complex. Two mathematical treatments methods of the experimental results were employed. From the results it can be concluded that this system corresponds to a mononuclear complex with 1:1:1 stoichiometry.

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The counteranion exchange of quaternary 1,2,3-triazolium salts was examined using a simple method that permitted halide ions to be swap for a variety of anions using an anion exchange resin (A¯ form). The method was applied to 1,2,3-triazolium-based ionic liquids and the iodideto- anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Additionally, an anion exchange resin (N3¯ form) was used to obtain the benzyl azide from benzyl halide under mild reaction. Likewise, following a similar protocol, bis(azidomethyl)arenes were also synthesized in excellent yields. The results of a proton NMR spectroscopic study of simple azolium-based ion pairs are discussed, with attention focused on the significance of the charged-assisted (CH)+···anion hydrogen bonds of simple azolium systems such as 1-butyl-3-methylimidazolium and 1-benzyl-3-methyl-1,2,3-triazolium salts.

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The counteranion exchange of quaternary 1,2,3-triazolium salts was examined using a simple method that permitted halide ions to be swap for a variety of anions using an anion exchange resin (A¯ form). The method was applied to 1,2,3-triazolium-based ionic liquids and the iodideto- anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Additionally, an anion exchange resin (N3¯ form) was used to obtain the benzyl azide from benzyl halide under mild reaction. Likewise, following a similar protocol, bis(azidomethyl)arenes were also synthesized in excellent yields. The results of a proton NMR spectroscopic study of simple azolium-based ion pairs are discussed, with attention focused on the significance of the charged-assisted (CH)+···anion hydrogen bonds of simple azolium systems such as 1-butyl-3-methylimidazolium and 1-benzyl-3-methyl-1,2,3-triazolium salts.